Polymer, process and composition

ABSTRACT

There are described vinyl sequential copolymers (and processes for making them) comprising (a) at least 8. 5 wt-% preferably &gt;=20 wt-% of a higher itaconate diester (preferably dibutyl itaconate—DBI); (b) less than 23 wt-% acid monomer but also sufficient to have an acid value less than 150 mg KOH/g of polymer, (c) optionally with less than 50 wt-% of other itaconate monomers, and (d) optionally less than 77 wt-% of other monomers not (a) to (c). The DBI may be biorenewable. One embodiment is an aqueous dispersion of the vinyl sequential polymer of two phases: A) 40 to 90 wt-% of a vinyl polymer A with Tg from −50 to 30° C.; and B) 10 to 60 wt-% of a vinyl polymer B with Tg from 50 to 130° C.; where DBI is used to prepare A and/or B and polymer A has from 0.1 to 10 wt-% of at least one acid-functional olefinically unsaturated monomer.

The present invention relates to polymers and polymeric materialsobtained and/or obtainable from certain 2-methylidenebutanedioatediester monomers (also referred to herein as higher itaconate diesters)to a process for making such a polymers and their use to prepare forexample coatings, inks and/or adhesives. It is preferred that polymersof the invention, and/or the higher itaconate diesters, are obtainedfrom bio-renewable sources.

Many conventional polymers often suffer from undue sensitivity to water.This is especially true for water based polymer emulsions which cansuffer from an increased water sensitivity compared to their solventborne counterparts. A common way of countering this is to incorporatevery hydrophobic monomers, such as butyl acrylate (BA) or 2-ethylhexylacrylate (EHA). However, as homopolymers from these monomers have anextremely low Tg, incorporation of large amounts of these monomersproduces a composition which is very often too soft (low Tg), yet is notsufficient hydrophobic if the amount of these monomer is sufficientlylow to produce a satisfactory Tg. This might in turn be mitigated byintroduction of high Tg, hydrophobic monomer such as styrene and thelike. However polymer compositions comprising stryenic monomers, sufferfrom reduced outdoor durability because of the inherent UV sensitivityof styrene.

We have now surprisingly found that the dilemma described above can besolved. Good water resistance and low water sensitivity combined withhigh hardness and high elongation at break may be achieved byintroducing higher ester itaconates such as dibutyl itaconate (DBI) asthe hydrophobic monomer. Even though these monomers are veryhydrophobic, the applicant has unexpectedly found that polymers madefrom higher itaconate esters do not suffer the same reduction inhardness typically observed for copolymers made from high concentrationsof the typical hydrophobic monomers such as butyl acryate (BA) and/or2-ethyl hexyl acrylate (EHA).

Itaconate ester monomers have been described for very many years.However they have not been widely used to make commercial vinyl polymersbecause they are expensive and difficult to process. Prior art documentsdescribe the use of itaconate esters only in general terms and typicallydescribe or exemplify lower itaconate diesters such as dimethylitaconate (DMI). The few documents which describe higher itaconateesters are described below.

U.S. Pat. No. 4,206,292 (Kureha Kagaku Kogyo Kabushiki Kaisha) describesa vinyl chloride resin coating with a smooth surface. The coatingcomprises: (1) 100 parts of vinyl chloride polymer; and (2) 0.1 to 30parts of a polymer processing aid comprising: (A) 10 to 100 parts of acopolymer comprising 20 to 99% of an alkyl methacrylate, 1 to 70% of adialkyl itaconate, and 0 to 60% of a copolymerizable monomer; and (B) 0to 90 parts of a copolymer comprising 80 to 100% of an alkylmethacrylate, and 0 to 20% of a copolymerizable monomer. The vinylchloride resins are not prepared from bio-based or other environmentallybenign sources. The maximum amount of DBI that is used in the examplesis 30% by weight.

U.S. Pat. No. 4,547,428 (Monsanto) describes a terpolymer comprisingrepeating units derived from an olefin, a diester of an additionpolymerizable unsaturated dicarboxylic acid, and a solubilizing monomerwhich promotes compatibility between the terpolymer and a vinyl halidepolymer. A granular form of the processing aid and a method for itspreparation are also disclosed. These polymers are not suitable forcoating applications and the highest concentration of DBI in theexamples is 17% by weight.

U.S. Pat. No. 4,588,776 (Monsanto) describes a polymer compositioncomprising a blend of a vinyl halide polymer and a particulateterpolymer having a molecular weight of at least 100,000 and a glasstransition temperature of at least 50° C. The terpolymer comprisesrepeating units derived from an olefin, a diester of an additionpolymerizable unsaturated dicarboxylic acid, and a solubilizing monomerwhich promotes compatibility of the terpolymer with the vinyl halidepolymer. These polymers are used to prepare shaped plastic articles andnot for coating applications. The maximum concentration of DBI used inthe examples is 17% by weight.

U.S. Pat. No. 6,951,909 (3M) describes a polymerizable system comprisesan organoborane, at least one polymerizable monomer, and a work-lifeextending agent. These compositions are not suitable for coatingapplications and the maximum concentration of DBI used in the examplesis 17% by weight.

WO11/073,417 (DSM) discloses an aqueous emulsion comprising at least avinyl polymer, said vinyl polymer comprising: a) 45 to 99 wt-% ofitaconate ester monomers having formula (I), wherein R and R′ areindependently an alkyl or an aryl group; b) 0.1 to 15 wt-% of ionic orpotentially ionic unsaturated monomers; c) 0 to 54 wt-% of unsaturatedmonomers, different from a) and b); and 0.9 to 54.9 wt-% by weight oftotal monomers of a chaser monomer composition added subsequently andpolymerised after the polymerisation of monomers a), b) and c); whereina)+b)+c) and the chaser monomer composition add up to 100 wt-%; andwherein the aqueous emulsion contains less than 0.5 wt-% free itaconateester monomers of formula I based on the total weight of the aqueousemulsion. Although it is a stated object of the invention to provide avinyl polymer with a high total concentration of itaconate estermonomers (see page 2, lines 14 to 17) in practise the larger proportionof such itaconate esters are lower itaconate esters (i.e. esters ofsmall alkyl groups such as DMI). This document does not teach that itwould be desirable to use a high concentration of higher itaconateesters (i.e. esters of large alkyl groups such as DBI). Indeed '417states that itaonate esters are difficult to process (see page 2, lines23 to 25) which combined with the teaching of the examples demotivates areader to incorporated large amounts of hydrophobic higher itaconateesters like DBI in a copolymer.

The only examples in '417 that describe use of a DBI monomer areExamples 2, 4, 5 and 6. The amounts of DBI and other monomers used toprepare these Examples is given in Table A below. It can be seen thatDBI is used as co-monomer only at a low concentrations in the finalcopolymer prepared in these Examples (at a maximum of 22.7 wt-%) whichare each also prepared with significant amounts of another hydrophobicmonomer butyl acrylate (BA). A styrene chaser monomer is always presentin the final product (at least 1,5 wt-%). These examples teach away fromusing DBI or other higher itaconate esters to replace common hydrophobicmonomers such as BA, EHA and/or styrene. No significant improvement isseen in film properties such as hardness and water sensitivity of thecopolymers prepared in this document.

GB1009486 (Borden) describes a latex of composite polymeric particleswhere the core and shell may comprise a copolymer of a vinylidenechloride and an ester of an alpha unsaturated aliphatic acid (the amountof ester in the shell being greater than the core). One example (Example3) describes use of dibutyl itaconate (DBI) as the ester in an totalamount of 17% by weight of total monomers (5% in the outer shell and 12%in an inner non core layer). These composite multi-layer polymerparticles address a problem of providing a water vapour barrier coatingfor paper and the like and they use much lower amounts of DBI than thepresent invention.

TABLE A (prior art DBI examples from WO11/073417) Monomers/wt-% (1 d.p.)Example Plex S Total of ′417 Composition AA BA MMA 652 DAAM MAA DMI DBI(chaser) Itaconate Ex 2 Initial feed 2.0 28.0 — — — — 45.0 25.0 — 60.0Single phase 1.8 25.2 — — — — 40.5 22.5 10.0  63.0 copolymer Ex 4 Firstfeed 4.4 32.4 13.2 — — — 20.0 30.0 — 50.0 Second feed 5.0 11.0 34.0 — —— 45.0 5.0 — 50.0 Sequential copolymer 4.1 25.5 15.8 — — — 22.7 22.7 9.145.4 Ex 5 First feed 4.2 30.0  9.5 8.4 — — 19.1 28.7 — 47.8 Second feed4.7  9.3 28.8 9.5 — — 42.9 4.7 — 47.6 Sequential copolymer 3.9 23.6 12.27.9 — — 21.8 21.8 8.7 43.6 Ex 6 Olg initial feed 35.4 — — — 8.0 5.0 51.6— — 51.6 Olg-plr initial feed — 41.2 — — — — 17.6 41.2 — 58.8 Polymer -oligomer 26.8 10.7 (inc 2.2 — — 6.1 3.8 42.7 8.5 1.5 51.2 BA chaser) InExamples 2, 4 and 5 of WO11/073417-the chaser monomer was 100 wt-%styrene, in Example 6 the chaser monomer composition was a mixture ofstyrene (40 wt-%) and BA (60 wt %).

U.S. Pat. No. 3,766,112 describes a high gloss latex for floor polishcomprising a chlorinated paraffin wax with a polyvinyl pyrrolidoneprotective colloid. Four monomer components used to prepare the colloid:styrene (70 to 85%), 2-ethylhexyl acrylate (EHA) (5 to 15%)(meth)acrylic acid (3 to 10%) and a fourth monomer (1 to 5%) allpercentages by weight of total monomers of the polyvinyl pyrrolidone.One of the seven monomers suggested as the fourth monomer is DBI. Thesepolymers address the problem of providing high gloss floor coatings andDBI is used in much lower amounts than in the present invention.

US2011-144265 (Durant Yvon) describes polymer particles prepared bypolymerising esters of itaconic acid in the presence of seed particlesto control particle size.

WO2002-068479 (3M) describes polymerisation of (meth)acrylic monomersusing a two part initator system of organoborane amine complex and anactivator. One of the many different examples (Example 6) is preparedfrom a low amount of DBI (20% by weight) and this example does not useany other itaconate diester monomer.

WO 2007-026949 (Nippon Cat.) describes emulsion resin compositions thathave a minimum film forming temperature (MFT) of ≦0° C. and are free ofvolatile organic compounds (VOC). These compositions are obtained bymixing a polymer with a high glass transition temperature (high Tg) witha polymer with low Tg. These polymers may be water dispersible and awide variety of carboxy acid fucnctional acid monomers are suggested toimpart such water solubility including itaconic acid, mono-methylitaconate ester and mono butyl itaconate ester (see page 12 lines 12 to14). No other itaconic acid derived monomers are described and a readerof this document would have no reason to incorporate (non carboxy-acidfunctional) itaconate diester monomers.

The esters (including both mono and di-esters) of2-methylidenebutanedioate (also referred to herein generically asitaconate esters) may be represented by Formula A:

where Ra and Rb can independently be H or any optionally substitutedhydrocarbo moiety (such as any aliphatic, cycloaliphatic or aromaticmoieties) provided that Ra and Rb are other than H (which is not anester but itaconic acid).

It has been found that certain hydrophobic itaconate diesters (e.g. diesters of large alkyl groups) are difficult to use in conventionalpolymerisation processes (especially in aqueous emulsion polymerisation)and are also expensive. Therefore there has been a reluctance to usesuch hydrophobic higher itaconate esters at high concentrations in suchprocesses.

It is an object of the present invention to solve some or all of theproblems identified herein for example by providing polymeric materialsmade from larger amounts of higher itaconate esters (such as DBI)optionally together with other olefinically unsaturated monomers (alsooptionally from a biorenewable source). The resultant polymers may havevarious additional advantages as well as those already described hereinsuch as good film forming at room temperature with the films having highflexibility (elasticity) and good resistance to blocking.

A second aspect of the present invention addresses the followingproblems in addition to or as well as those described herein.Traditional coatings may be unsatisfactory because the conventionalcoating films made from hard polymers possess little flexibility andwhen coated on substrates which are not dimensionally stable (such aswood) the coating can tear and chip off. To improve the processing ofdispersions of hard polymers large amounts of ingredients are added toassist film forming. When used in high concentrations these film formersare still present in the binder film in the coating and are releasedonly gradually by conventional polymers at room temperature. Thiscreates a high initial block resistance, which is the tendency offreshly applied coatings to block if they have dried for only a shorttime. High initial block resistance makes it virtually impossible tostack freshly coated substrates rapidly as when dried at roomtemperature their final block resistance is usually reached only afterseveral days.

EP 387664 discloses an aqueous synthetic resin dispersion having aminimum film forming temperature below 50° C. containing an emulsionpolymer with a core/shell structure consisting of A) 65-90% by weight ofa weakly crosslinked core polymer having a glass transition temperaturebelow 0° C. and an extension at break of at least 150% and B) 10-35% byweight of an essentially non-crosslinked shell polymer having a glasstransition temperature below 60° C., the glass transition temperature ofsaid core polymer being at least 10° C. below that of said shellpolymer.

U.S. Pat. No. 5,021,469 discloses a binder, for water based gloss paintscontains, dispersed in a aqueous phase, particles of a multiphaseemulsion polymer made up of (a) core material having a glass transitiontemperature exceeding 40° C. and (b) a shell material having a glasstransition temperature of less than 70° C.

U.S. Pat. No. 4,654,397 discloses a process for the preparation ofaqueous polymer dispersions which have a low film-forming temperaturebut still give films having a high block resistance, and the use ofthese polymer dispersions as binders for coating materials.

None of the above documents describe dispersions having the selectedcombination of features and integers as defined herein to produce theadvantageous combination of properties as discussed herein.

This second aspect of the invention has as its preferred object toprovide a physically-drying binder in the form of an aqueous syntheticresin dispersion which physically dries at low temperatures to givehighly elastic films which are more or less non-tacky from thebeginning. The emulsion polymers according to this second aspect of theinvention address some or all of the problems described herein.

Therefore broadly in accordance with the present invention there isprovided a copolymer (optionally a sequential copolymer) compositioncomprising (preferably consisting essentially of):

-   -   (a) greater than 8.5 wt-%, usefully ≧15 wt-%, preferably at        least 20 wt-%, more preferably at least 24 wt-%, more preferably        at least 30 wt-% for example at least 45 wt-% of at least one        monomer represented by Formula 1

-   -   -   where both R₁ and R₂ independently represent an optionally            substituted hydrocarbo moiety having from 4 to 10 carbon            atoms.

    -   (b) optionally at least one hydrophilic monomer preferably in an        amount less than 23 wt-%, more preferably 0.5 to 15 wt-%, and        also in an amount sufficient that the resultant polymer has an        acid value of from 0 to 150 mg KOH/g, preferably less than 150        mg KOH/g, more preferably from 3 to 100 mg KOH per g of polymer,

    -   (c) optionally less than 50 wt-%, for example from 0.01 to 10        wt-% and/or one or more monomers represented by Formula 2

-   -   -   (Formula 2 including itaconate diester monomers being other            than those represented by Formula 1)        -   where R₃ and R₄ independently represent H or an optionally            substituted hydrocarbo moiety having from 1 to 20 carbon            atoms        -   X₁ and X₂ independently represents O or NR₅ where R₅ denotes            H or an optionally substituted hydrocarbo moiety having from            1 to 20 carbon atoms with the proviso that when X₁ and/or X₂            are 0 then the respective R₃ and/or R₄ attached to the oxy            group independently represent an optionally substituted            hydrocarbo having from 1 to 3 carbon atoms

    -   (d) optionally less than 80 wt-%, usefully less than 77 wt-%,        preferably less than 75 wt-%, more preferably <70 wt-%, most        preferably <65% wt-% of monomers other than components (a), (b)        or (c).

    -   where the weight percentages (also denoted herein as “% by        weight” and/or “wt-%”) of amounts of (a), (b) (c) (d) are        calculated as a proportion of the total (weight) amount of        (a)+(b)+(c)+(d) which thus totals 100%.

Copolymers of the invention may also be limited by one or more of thefollowing optional provisos:

-   -   (I) when component (a) consists of DBI in an amount of less than        30% by weight of the total monomers then the copolymer is        substantially free of any chloro groups; and    -   (II) when component (a) consists of DBI in an amount of less        than 23% by weight of the total monomers then the copolymer is        prepared by other than an emulsion polymerisation method in        which a chaser monomer is used; and    -   (III) when component (a) consists of DBI in an amount of less        than 23% by weight of the total monomers then if component (d)        is present, component (d) is other than styrene or a mixture        consisting of butyl acrylate (60 wt-% of mixture) and styrene        (40 wt-% of mixture)    -   (IV) the copolymer is substantially free of styrene (preferably        styrene free), more preferably component (d) if present is other        than styrene or a mixture consisting of butyl acrylate (60 wt-%        of mixture) and styrene (40 wt-% of mixture), more preferably        component (d) if present is other than styrene (S), butyl        acrylate (BA), 2-ethyl hexyl; acrylate (EHA) or mixtures        thereof.    -   (V) is prepared by other than an emulsion polymerisation method        in which a chaser monomer is used; and    -   (VI) the copolymer is prepared by other than an emulsion        polymerisation method in which a chaser monomer is used        optionally this proviso applying only when component (a)        consists of DBI preferably in an amount of from 8.5 to 15% by        weight of the total monomers (a)+(b)+(c)+(d).    -   (VII) when component (a) consists of DBI then component (a) is        present in an amount other than 8.5 wt-%, 21.8 wt-%, 22.5 wt-%        or 22.7 wt % of the total monomer composition, preferably other        than from 8 wt-% to 23 wt %,    -   (VIII) when component (a) consists of DBI then component (a) is        present in an amount other than 4.7 wt-%, 5.0 wt-%, 8.5 wt-%,        21.8 wt-%, 22.5 wt-%, 22.7 wt %, 25.0 wt-%, 28.7 wt-%, 30.0 wt-%        or 41.2 wt-% of the total monomer composition, preferably other        than from 4 wt-% to 42 wt %,    -   (IX) the copolymer is obtained other than from a polymerisation        of a dimethyl itaconate (DMI) and dibutyl itaconate (DBI) in the        respective weight ratio of 15 to 85 in the presence of poly        diethyl itaconate seed polymer; more preferably the copolymer is        obtained other than from polymerisation of dialkyl itaconate(s)        in the presence of a poly diethyl itaconate seed polymer; most        preferably the copolymer is obtained other than from        polymerisation in the presence of a poly dialkyl itaconate seed        polymer;    -   (X) if polymerisation of the copolymer occurs in the presence of        an initator system comprising organoborane amine complex and an        activator then component (a) is present in an amount greater        than 20 wt-%, preferably at least 24 wt-% of total monomers        (a)+(b)+(c)+(d).

Preferably the copolymer of the invention is a sequential copolymer. Asused herein the term sequential copolymer denotes a polymer obtainedand/or obtainable by polymerisation of different polymer precursors(e.g. monomers) in sequence, for example in a living anionicpolymerisation and/or emulsion polymerisation. A sequential polymer maybe prepared in separate steps and/or in a single step for example by anall in one polymerisation where all the required ingredients are alreadypresent in the same vessel. Sequential copolymers of the invention mayhave any suitable distribution of monomers within the copolymer, forexample be statistic, random, gradient, alternating, periodic and/orblock copolymers.

Preferably the sequential copolymer composition is an emulsion copolymer(usefully an emulsion polymer prepared where no chaser monomer has beenused), more preferably an aqueous emulsion copolymer, most preferably anaqueous coating composition.

Conveniently the composition is substantially free of polyvinyl chloridepolymer and/or chlorinated paraffin wax, more preferably issubstantially free of any monomer comprising chloro groups, mostpreferably is substantially free of any species comprising Cl whether asa substituent, atom, di-molecule, ion or otherwise

Broadly there is provided in a yet further aspect of the presentinvention a process for preparing a copolymer comprising the step ofpolymerising polymer precursors in a polymerisation method the polymerprecursors comprising component (a), component (b) and optionallycomponent (c) and/or component (d) as described above.

Preferably the polymerisation method is selected from an emulsion and/orsuspension polymerisation. More preferably the copolymer is an emulsioncopolymer.

Another aspect of the invention broadly provides for an optionallycopolymer obtained and/or obtainable by a process of the presentinvention.

Hydrophobic Component (a) (Higher Itaconate Esters)

The present invention is particularly concerned with polymers obtainedand/or obtainable from a narrow class of itaconate diester monomersselected from the broad disclosure of general itaconate esters ofFormula A. Thus the hydrophobic component (a) comprises itaconatediester(s) of Formula 1:

where both R₁ and R₂ independently represent an optionally substitutedhydrocarbo moiety having from 4 to 10, preferably from 4 to 8, morepreferably from 4 to 6, most preferably 4 carbon atoms.

The diesters of Formula 1 are also referred to herein as higheritaconate diesters.

Usefully R₁ and R₂ may independently represent optionally substitutedC₄₋₁₀alkyl and/or C₄₋₁₀aryl, more usefully C₄₋₈alkyl and/or C₄₋₈aryl andmost usefully C₄₋₆alkyl, even more usefully butyl (n-butyl beingespecially useful).

Whilst R₁ and R₂ may be different, more conveniently they representidentical moieties. Especially preferred examples of Formula 1 includethose where R₁ and R₂ are identical, such di(benzyl)itaconate,di(phenyl)itaconate, di-n-butyl itaconate, di-i-butyl itaconate, and/ordi-2-ethyl hexyl itaconate. Where R₁ and R₂ both represent n-butylFormula 1 represents dibutyl 2-methylidenebutanedioate (also referred toherein as di(n-butyl)itaconate or DBI) which has the followingstructure:

DBI is the most preferred monomer for use as component (a) in thepresent invention.

Preferably component (a) is used in a total amount of at least 40%, andmore preferably at least 50% by weight of the total monomers.

The itaconate functional component (a) is present in the compositionsand/or copolymers of the invention in an amount of greater than 8.5%wt-%, usefully 15 wt-%, preferably at least 20 wt-%, usefully at least24 wt-%, more usefully at least 30 wt-%, even more usefully at least 35wt-% and most usefully at least 40 wt-%, for example at least 50% basedon the total weight of monomers (a), (b), (c) and (d) used to preparethe copolymer being 100%.

Conveniently the itaconate functional component (a) may be present inthe compositions and/or copolymers of the invention in an amount of lessthan 80 wt-%, more conveniently less than 70 wt-%, even moreconveniently less than 65 wt-%, most conveniently less than 58 wt-%, andfor example less than 55 wt-%; based on the total weight of monomers(a), (b), (c) and (d) used to prepare the copolymer being 100%.

Preferably the itaconate functional component (a) may be present in thecompositions and/or copolymers of the invention in an amount of from 20to 80 wt-%, more preferably from 24 to 70 wt-%, even more preferablyfrom 30 to 65 wt-%, most preferably from 35 to 65 wt-%, for example from40 to 55 wt-% based on the total weight of monomers (a), (b), (c) and(d) used to prepare the copolymer being 100%.

Hydrophilic Component (b) (Acid Functional Monomers)

Suitable hydrophilic monomers of component (b) are those that areco-polymerisible with the hydrophobic monomer(s) of component (a) andare water soluble. Conveniently the at least one hydrophilic monomer ofcomponent (b) may comprise at least one activated unsaturated moiety asdefined herein.

Usefully the hydrophilic monomer of component (b) is an acid functionalethylenically unsaturated monomer for example an acid functional acrylicmonomer.

It will be understood that when referring to acid functional and/oracidic components herein this may relate to acidic moieties and/orpotential acidic moieties which under the conditions of use may formacidic groups (e.g. anhydrides). An acid bearing monomer could bepolymerised as the free acid or as a salt, e.g. the ammonium and/oralkali metal salt thereof. References herein to acids should thereforealso be understood to include suitable salts and/or derivates thereof(such as anhydrides and/or acid chlorides thereof).

Preferred hydrophilic monomers comprise, advantageously consistessentially of, at least one ethylenically unsaturated carboxylic acidalthough other acid groups such as optionally substituted organophosphoric and/or sulphonic acids may also be used.

Examples include phosphated alkyl (meth)acrylates, sulphonic acids (andderivatives thereof) of arylalkylenes, sulphonic acids (and derivativesthereof) of alkyl (meth)acrylates and/or other organo substitutedsulphonic acids (such as acrylamidoalkyl sulfonic acids).

Preferred arylalkylene sulphonic acids are those where the arylalkylenemoiety comprises optionally hydrocarbo substituted styrene, convenientlyoptionally C₁₋₁₀hydrocarbyl substituted styrene more convenientlyoptionally C₁₋₄alkyl substituted styrene. Useful acids are sulphonicacid substituted derivatives of stryenic compounds selected from thegroup consisting of styrene, α-methyl styrene, vinyl toluene, t-butylstyrene, di-methyl styrene and/or mixtures thereof. Especially preferredis styrene p-sulphonic acid and its corresponding acid chloride styrenep-sulphonyl chloride.

Preferred phosphated organo acids comprise phosphated (meth) acrylatesoptionally substituted for example with one or more hydroxyl groups, forexample phosphated hydroxy(meth)acrylates and C₁₋₄alkyl esters thereof.

Other preferred hydrophilic monomers of component (b) comprises partialacids of multivalent esters, more preferably. half esters of diesters,most preferably mono acid half itaconate esters (i.e. those esters ofFormula A where either R_(a) or R_(b) is H). Itaconic acid is alsoanother example of a (di)acid functional monomer which is also suitableas component (b).

More preferred acids have one ethylenic group and one or two carboxygroups. Most preferably the acid(s) (and/or suitable acid derivative(s)thereof) are selected from the group consisting of: acrylic acid (andcopolymerisable oligomers thereof), beta carboxy ethyl acrylate,citraconic acid, mesaconic acid, crotonic acid, fumaric acid, itaconicacid, maleic acid, methacrylic acid, methylene malonic acid, anhydridesthereof, salts thereof, acid chlorides thereof, combinations thereof inthe same species and/or mixtures thereof.

Especially preferred monomers that may comprise component (b) areselected from:

acrylic acid, methacrylic acid, beta carboxy ethyl acrylate, methylenemalonic acid, maleic anhydride, itaconic acid, itaconic anhydride,phosphated hydroxyl ethyl methacrylate (phosphated HEMA), phosphatedhydroxylethyl acrylate (phosphated HEA), phosphated hydroxylpropylmethacrylate (phosphated HPMA), phosphated hydroxylpropyl acrylate(phosphated HPA), sulphonated styrene (and its chloride),2-acrylamido-2-methylpropane sulfonic acid (AMPS) andethylmethacrylate-2-sulphonic acid.

Particularly preferred acid monomers are acrylic acid, methacrylic acid,beta carboxy ethyl acrylate, itaconic acid, and/or itaconic anhydride.

For emulsion polymerization acrylic acid, methacrylic acid, beta carboxyethyl acrylate, and/or itaconic acid may be convenient. For SADcopolymerization, acrylic acid, methacrylic acid, and/or itaconicanhydride are preferred.

The hydrophillic monomer component (b) may optionally be absent from thecompositions and/or copolymers of the invention but if present ispresent in an amount of more than a trace amount usefully greater thanor equal to 0.1 wt-%, conveniently greater than or equal to 0.5 wt-%,for example greater than 0.8 wt-% based on the total weight of monomers(a), (b), (c) and (d) used to prepare the copolymer being 100%.

Conveniently component (b) if present is present in the compositionsand/or copolymers of the invention in an amount of less than 23 wt-%,more conveniently less than or equal to 20 wt-%, even more convenientlyless than or equal to 10 wt-%, most conveniently ≦5 wt-%, such as ≦3wt-%; for example 51 wt % based on the total weight of monomers (a),(b), (c) and (d) used to prepare the copolymer being 100%.

Preferably, component (b) may be used in a total amount from 0 to 10wt-%, more preferably from about 0.1 to about 5 wt-%, even morepreferably from about 0.1 to about 3 wt-%, most preferably from about0.5 to about 1% by weight based on the total weight of monomers (a),(b), (c) and (d) used to prepare the copolymer being 100%.

Conveniently component (b) may be used in a total amount sufficient thatthe resultant polymer has an acid value (AV) of between 3 and 100 mg KOHper g of solid polymer, preferably from 8 to 80 mg KOH per g, morepreferably from 15 to 65 mg KOH per g, and most preferably from 15 to 45mg KOH per g.

Usefully component (b) satisfies both the acid value (AV) and weightlimits herein, but it will be appreciated that depending on the monomerused the AV specified herein may be achieved using weight percentagesoutside those preferred wt-% values given herein. Where there is anapparent inconsistency herein between any weight % of monomer or othercomponent and the acid values specified it will be appreciated thatsatisfying the AV is generally the more desirable objective. Ifnecessary the values for weight % of the relevant ingredients can bemodified appropriately in a manner well known to a skilled person.

Component (c) (Lower Itaconate Esters and Itaconate Amides)

Component (c) comprises one or more other diester itaconate monomersother than those of Formula 1, preferably a monomer of Formula A whereneither Ra nor Rb are H or an optionally substituted C₄₋₁₀hydrocarbo.More preferably component (c) comprises a lower itaconate diester. Asused herein the term lower itaconate diester denotes diesters of FormulaA where Ra and Rb are independently optionally substitutedC₁₋₃hydrocarbo groups, such as C₁₋₃alkyl, an example of which isdimethyl itaconate (DMI).

Usefully component (c) may comprise lower itaconate diesters (i.e.diesters other than those of Formula 1), and/or higher or loweritaconate amides and thus component (c) may be represented by Formula 2

where R₃ and R₄ independently represent H or an optionally substitutedhydrocarbo moiety having from 1 to 20 carbon atoms (e.g. from 1 to 6carbon atoms); preferably C₁₋₂₀alkyl, preferably C₁₋₆alkyl, morepreferably C₁₋₄alkyl, most preferably C₁₋₃alkyl; X₁ and X₂ independentlyrepresents O or NR₅ where R₅ denotes H or an optionally substitutedhydrocarbo moiety having from 1 to 20 carbon atoms (e.g. from 1 to 6carbon atoms); preferably C₁₋₂₀alkyl, more preferably C₁₋₆alkyl; evenmore preferably C₁₋₄alkyl; for example C₁₋₃alkyl;with the proviso that when X₁ and/or X₂ are 0 then the respective R₃and/or R₄ attached to the oxy group independently represent anoptionally substituted hydrocarbo having from 1 to 3 carbon atoms,preferably C₁₋₃alkyl.

Components (a), (b), (c) and (d) are mutually exclusive. Thus compoundsof Formula 2 are different from those of Formula 1 and the mono acidhalf itaconate esters are also excluded from Formulae 1 and 2,optionally comprising part of hydrophilic component (b).

Thus in one preferred embodiment of the invention components(a) and (b)(and optionally (c) where present) are each derived from itaconatesand/or acids and/or derivatives thereof, more preferably from abiorenewable source. Thus for example component (a) may be adi(C₄₋₆dialkyl)itaconate, (e.g. DBI), component (b) may be itaconicanhydride itaconic acid, and/or C₁₋₄alkyl monoester of itaconic acid andcomponent (c) where present may be a di(C₁₋₃dialkyl)itaconate (e.g.DMI). In such an embodiment optionally there is no component (d) so thecopolymer may advantageously be obtained from monomers from the sameitaconate source.

Whilst R₃ and R₄ may be different, more conveniently they representidentical moieties.

Whilst X₁ and X₂ may be different, more conveniently they representidentical moieties.

Preferably component (c) may be used in a total amount of less than 35%,more preferably from 0 to 25% by weight.

The component (c) if present may optionally be present in an amountusefully greater than or equal to 0.1 wt-%, conveniently greater than orequal to 0.5 wt-%, for example greater than 1.0 wt-% based on the totalweight of monomers (a), (b), (c) and (d) used to prepare the copolymerbeing 100%.

Conveniently component (c) is present in the compositions and/orcopolymers of the invention in an amount of less than 40 wt-%, moreconveniently less than or equal to 35 wt-%, even more conveniently lessthan or equal to 25 wt-%, most conveniently ≧20 wt-%, for example ≧15 wt% based on the total weight of monomers (a), (b), (c) and (d) used toprepare the copolymer being 100%.

Component (c) may be used in a total amount from 0 to 10 wt-%,preferably from 0.01 to 10 wt-%, more preferably from 0.1 to 40 wt-%,even more preferably from 0.5 to 35 wt-%, most preferably from 1.0 to 30wt-%, for example from 1.0 to 25 wt-% by weight based on the totalweight of monomers (a), (b), (c) and (d) used to prepare the copolymerbeing 100%.

Component (d) (Other Copolymerisable Monomers)

Preferably component (d) comprises monomers not part of components (a),(b) or (c), more preferably that are copolymerisable with them in anysuitable technique such as any of those described herein (for example ina SAD and/or an emulsion polymerisation).

Component (d) may comprise a suitable activated unsaturated moiety (suchas ethylenic unsaturation) where the structure(s) of component (d) donot overlap with any of components (a), (b) or (c).

Preferably component (d) is used in an amount of less than 50% and morepreferably less than 40% by weight.

Component (d) may comprise monomers that can undergo crosslinking, thatcan improve adhesion of the coating to various substrates, that canenhance the colloidal stability of the polymer emulsion, or that can beused to affect Tg, or polymer polarity.

Conveniently component (d) may comprise (meth)acrylate monomers havingalkyl moieties comprising between 1 and 20 carbon atoms, styrene,alpha-methyl styrene, (meth)acrylonitrile, (meth)acryl amide oralkylated (meth)acryl amides, diacetone acryl amide, acetoacetoxyethylmethacrylate, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate,silane functional monomers, such as 3-methacryloxypropyltrimethoxysilane (Geniosil GF31, ex Wacker), ureido functional monomers,such as Plex 6852-O (ex. Evonik), i-bornyl (meth)acrylate, polyethylene(meth)acrylate, polypropylene (meth)acrylate.

Component (d) may also comprise crosslinking monomers that can inducecrosslinking of the copolymer composition. Crosslinking can occur atambient temperatures (using for instance diacetone acryl amide combinedwith adipic dihydrazide), at elevated temperatures (stoving conditionsin which for instance copolymerized hydroxyethyl (meth)acrylate reactswith hexamethoxy methyl melamines), as 2C composition (copolymerizedhydroxyethyl (meth)acrylate reacting with polyisocyanates, such asBayhydur 3100), or as UV coating (when polymers or oligomers havingmultiple unsaturated groups are admixed. Typical examples include di- ortri-functional multifunctional acrylates such as trimethylol propanetriacrylate or ethoxylated or propoxylated versions thereof).

Optionally component (d) may also comprise least one polymerprecursor(s) of Formula 3

where Y denotes an electronegative group,R₆ is H, OH or an optionally hydroxy substituted C₁₋₁₀hydrcarboR₇ is H or a C₁₋₁₀hydrocarbo;R₈ is a C₁₋₁₀hydrocarbo group substituted by at least one activatedunsaturated moiety; and; either:A represents a divalent organo moiety attached to both the —HN— and —Y—moieties so the -A-, —NH—, —C(═O)— and —Y— moieties together represent aring of 4 to 8 ring atoms, and R₇ and R₈ are attached to any suitablepoint on the ring; orA is not present (and Formula 3 represents a linear and/or branchedmoiety that does not comprise a heterocyclic ring) in which case R₇ andR₈ are attached to R₆; andm is an integer from 1 to 4.

The ring moiet(ies) of Formula 3 are each attached to R₈ and in Formula3 when m is 2, 3 or 4 then R₈ is multi-valent (depending on the value ofm). If m is not 1 R₇ and —Y— may respectively denote the same ordifferent moieties in each ring, preferably the same respective moietiesin each ring. R₇ and R₉ may be attached at any suitable position on thering.

Preferred monomers of Formula 3 comprise, conveniently consistessentially of, those where: A represents a optional substituteddivalent C₁₋₅hydrocarbylene; and

—Y— is divalent —NR₉— (where R₉ is H, OH, optionally hydroxy substitutedC₁₋₁₀hydrocarbo or R₈) or divalent O,

More preferred monomers of Formula 3 comprise those where: m is 1 or 2

—Y— is —NR₈— (i.e. where Formula 2 is attached to R₉ via a ringnitrogen), A represents a divalent C₁₋₃hydrocarbylene; R₆ is H, R₇ is aC₁₋₁₀hydrocarbo; andR₈ comprises a (meth)acryloxyhydrocarbo group or derivative thereof(e.g. maleic anhydride).

Monomers represented by Formula 3 include some monomers informallyreferred to as ureido monomers. Further suitable ureido monomers ofFormula 3 are described in “Novel wet adhesion monomers for use in latexpaints” Singh et al, Progress in Organic Coatings, 34 (1998), 214-219,(see especially sections 2.2 & 2.3) and EP 0629672 (National Starch)both of which are hereby incorporated by reference. Conveniently themonomers of Formula 3 may be used as a substantially pure compound (ormixture of compounds) or may be dissolved in a suitable solvent such asa suitable (meth)acrylate or acrylic derivative for example methylmethacrylate.

Other and/or additional component (d) may be used in those cases wherehigher molecular weights are desired, such as suitable multi functional(meth)acrylates or divinyl aromatics. Typical examples include di-,tri-, or tetra-functional (meth)acrylates, especially difunctional(meth)acrylates and divinyl benzene. Typical concentrations are lessthan 10%, more preferred less than 5%, even more preferred between 0.05and 4%, most preferred between 0.1 and 2.5%, and even most preferredbetween 0.15 and 1.5% by weight based on total monomers.

The component (d) may optionally be present in an amount usefullygreater than or equal to 0.1 wt-%, conveniently greater than or equal to0.5 wt-%, for example greater than 1.0 wt-% based on the total weight ofmonomers (a), (b), (c) and (d) used to prepare the copolymer being 100%.

Conveniently component (d) is present in the compositions and/orcopolymers of the invention in an amount of less than 77 wt-%, moreconveniently less than or equal to 50 wt-%, even more conveniently lessthan or equal to 40 wt-%, most conveniently ≦30 wt-%, for example ≦25 wt% based on the total weight of monomers (a), (b), (c) and (d) used toprepare the copolymer being 100%.

Preferably, component (d) may be used in a total amount from 0 to 77wt-%, more preferably from about 0.1% to about 50 wt-%, even morepreferably from about 0.5% to about 40 wt-%, most preferably from about1.0% to about 30% by weight based on the total weight of monomers (a),(b), (c) and (d) used to prepare the copolymer being 100%.

One aspect of the invention relates to an aqueous sequential vinylpolymer dispersion comprising 30% by weight (preferably at least 40%) ofpolymer obtained or obtainable from one or more higher itaconatediester(s).

Other examples of suitable monomers that may comprises all or part ofcomponents (a), (b), (c), or (d) may be described in the various furtheraspects of the invention later in this application. It will beunderstood that where suitable such monomers where not already mentionedabove may also be used as components in the above aspect of theinvention.

Polymerisation Processes

Copolymers (optionally sequential copolymers) of the invention may beformed using a number of processes. These include emulsionpolymerisation, suspension polymerisation, bulk polymerisation andsolution polymerisation. Such processes are extremely well known andneed not be described in great detail.

In one embodiment emulsion polymerisation is used to form copolymers ofthe invention.

A conventional emulsion process involves dispersing the monomers in anaqueous medium and conducting polymerisation using a free-radicalinitiator (normally water soluble) and appropriate heating (e.g. 30 to120° C.) and agitation.

The aqueous emulsion polymerisation can be effected with conventionalemulsifying agents (surfactants) being used such as anionic and/ornon-ionic emulsifiers. The amount used is preferably low, preferably 0.3to 2% by weight, more usually 0.3 to 1% by weight based on the weight oftotal monomers charged.

The aqueous emulsion polymerisation can employ conventional free radicalinitiators such as peroxides, persulphates and redox systems as are wellknown in the art. The amount of initiator used is generally 0.05 to 3%based on the weight of total monomers charged.

The aqueous emulsion polymerisation process may be carried out using an“all-in-one” batch process (i.e. a process in which all the componentsto be employed are present in the polymerisation medium at the start ofpolymerisation) or a semi-batch process in which one or more of thecomponents employed (usually at least one of the monomers), is wholly orpartially fed to the polymerisation medium during the polymerisation.Although not preferred, fully continuous processes could also be used inprinciple. Preferably a semi-batch process is employed for example powerfeed polymerization which is a semi-continuous emulsion copolymerizationin which the instantaneous composition of the formed copolymer is thesame as that of the added monomer mixture(s). Power feed polymerisationis typically used to make gradient polymers. Sequential copolymers ofthe invention may also be prepared from a dispersion of a first(co)polymer that is mixed with further unpolymerised polymer precursoror monomer which is then polymerised in the present of the firstpolymer.

The polymerisation technique employed may be such that a low molecularweight polymer is formed, e.g. by employing a chain transfer agent suchas one selected from mercaptans (thiols), certain halohydrocarbons andalpha-methyl styrene; or catalytic chain transfer polymerisation usingfor example cobalt chelate complexes as is quite conventional.Alternatively a controlled radical polymerisation process can be used,for instance by making use of an appropriate nitroxide or athiocarbonylthio compounds such as dithioesters, dithiocarbamates,trithiocarbonates, and xanthates in order to mediate the polymerizationvia for example a nitrox mediated polymerisation (NMP), a reversibleaddition fragmentation chain-transfer process (RAFT) or atom transferradical polymerization (ATRP).

When the copolymer of the invention is an emulsion polymer it may bemixed with a variety of other polymer emulsions such as those that donot comprise DBI (or higher itaconate esters). Examples of such secondpolymer emulsions can be polyurethane emulsions,polyurethane-poly(meth)acrylate emulsions, alkyd emulsions, polyesteremulsions and/or polyvinyl emulsions. This latter group of copolymeremulsions may comprise oligomer-polymer emulsions, gradient morphologyemulsions, sequentially polymerized emulsions, or single phase copolymeremulsions.

The emulsions according to the description above can be produced viaemulsion polymerization or via a process called solvent assisteddispersion (SAD) polymerization.

When the copolymer emulsion is produced via emulsion polymerization thiscan be according to a single feed process, a sequentially fedmulti-phase copolymerization process, an oligomer supported emulsionpolymerization process or a power feed process, resulting in a gradientparticle morphology.

In the case of solvent assisted dispersion polymerization process, orSAD polymerization, the polymerization is performed in organic solvents.Next, base and/or surfactant are added and the polymer solution isemulsified. Preferably, the solvent is removed via evaporation at theend of the complete process.

SAD polymer emulsions can be produced via as single feed solutionpolymerization or by a sequentially fed multi-phase polymerization. Itis also envisaged that an SAD polymer emulsion, prior or after theoptional removal of the solvent, is used as a seed for an emulsionpolymerization stage. In this case, the polymer emulsion preparedaccording to the SAD process is used as seed in a batch or semi-batchpolymerization process.

The preferred polymerization process is emulsion polymerization.

Preferably, the weight average molecular weight (M_(w)) (as determinedwith GPC as described herein) of the DBI containing copolymers is morethan 2000 g/mol, more preferably more than 10,000 g/mol, even morepreferably more than 25,000 g/mol, most preferably more than 40,000g/mol, and even most preferably more than 100,000 g/mol.

In the case of oligomer-polymer emulsions prepared via emulsionpolymerization lower molecular weights may be desired. In those caseschain transfer agents may be employed. Typical chain transfer agents canbe mercaptans, such as lauryl mercaptan, i-octyl thioglycolate, or3-mercapto propionic acid, or halogenides, such as bromomethane,bromoethane. Typical chain transfer concentrations in these cases areenough to reduce the weight average molecular weight of the oligomerphase to between 500 and 100,000 g/mol, more preferred between 1,000 and60,000 g/mol, even more preferred between 2,500 and 50,000 g/mol, andmost preferred between 5,000 and 25,000. Typical chain transfer agentconcentrations are below 5%, more preferably below 2.5%, and mostpreferably between 0.5 and 2.5% by weight of total monomer. In the casethat the oligomer is combined with a high molecular weight polymer, thepreferred molecular weights for the high molecular weight fraction willbe as described earlier.

In those cases where the copolymer emulsion comprises multiple phases oris made up from multiple monomer feeds (sequential, oligomer-polymer orpower feed) one of the copolymer phases preferably comprises between 10and 80%, more preferably between 15 and 50%, and most preferably between20 and 40% by weight of the total monomers used to prepare thesequential, power feed, and/or oligomer-polymer composition. Thisparticular copolymer phase has a Tg, as calculated using the Foxequation, of higher than 40° C., more preferably higher than 60° C., andmost preferably higher than 80° C. The other copolymer phase(s) may thencomprise between 20 and 90% of the total monomers more preferablybetween 50 and 85%, and most preferably between 60 and 80% by weight ofthe total monomers used to prepare the sequential, power feed, and/oroligomer-polymer composition. These particular copolymer phase(s) have aTg, as calculated using the Fox equation, of less than 40° C., morepreferably of less than 20° C., and most preferably of less than 0° C.

The difference in Tg in such emulsions between that of the high Tgphase(s) and that of the low Tg phase(s) is preferably at least 20° C.,more preferably at least 30° C., and most preferably at least 40° C.

In a special case it is envisaged that the itaconic anhydride which iscopolymerized in an SAD copolymerization process can be post modifiedusing chemicals having anhydride reactive groups. The objective in thesecases is to introduce special functionalities, such as crosslinking oradhesion promoting groups, while maintaining an acid group that can beused for colloidal stabilization.

Modification of the anhydride groups can occur with any nucleophilicfunctionality. Preferred functionalities include hydroxyl groups,hydrazide groups, hydrazine groups, semi-carbazide groups and aminegroups. In all cases, modification will result in the introduction ofthe moiety attached to the hydroxyl, hydrazide, hydrazine,semi-carbazide or amine group and, simultaneously, of an acid group. Theacid group can subsequently be used for emulsifying the copolymer.

The modification can be done with monofunctional hydroxyl groups,hydrazide, or hydrazine, or primary, or secondary amines, but also withdi-functional or higher functional hydroxyl, hydrazine, hydrazide,semi-carbazide, or primary or secondary amines. Potential hydroxylfunctionalities can include C₁-C₂₀ aliphatic, aromatic, orcycloaliphatic mono-, di-, or high functional alcohols. The aliphatic,aromatic, or cycloaliphatic groups can include other functionalitiesthat can, for instance, be used for improved adhesion, crosslinking orother purposes. Typical examples of such functionalities can includephosphate, phosphonate, sulphate, sulphonate, ketone, silane, (cyclic)ureido, (cyclic) carbonate, hydrazide, hydrazine, semi-carbazide,urethane, urea, carbamate, and melamine

The preferred (poly)amines, (poly)hydrazines, or (poly)hydrazides can becharacterized by the same description.

In the case where the copolymer composition is prepared via emulsionpolymerization, the pH of the emulsion can preferably be increased usingorganic or inorganic bases. Typical examples include ammonia, primaryand secondary organic amines, lithium hydroxide, sodium hydroxide orpotassium hydroxide, sodium carbonate or sodium bicarbonate. Typically,the pH is increased only at the end of the manufacturing process,although it can be envisaged that either at the start of thepolymerization the pH of the aqueous phase is already increased(buffered) or that the pH of a polymerizing mixture is increased forinstance between sequential monomer feeds. In the case of copolymersprepared via emulsion polymerization the pH is preferably increased atthe end of the manufacturing process, preferably using ammonia orlithium hydroxide.

Typically, the pH is raised to values above 5, more preferred above 6,and most preferred to values of between 6 and 9.

When the copolymer emulsion is prepared via the SAD polymerizationprocess, emulsification can be done by addition of surfactants, but ispreferably done by first neutralizing the polymer acid groups. This canbe done by addition of base to the solution polymerized polymer followedby the addition of water or by addition of base to an aqueous phasefollowed by the addition of the polymer solution. In both cases,suitable bases are the same as above. Preferred bases are ammonia,lithium hydroxide or dimethyl ethanol amine, diethanol methyl amine,diethanol ethyl amine, diethyl ethanol amine and the like. Typically,the molar ratio of base to acid groups is between 0.5 and 1.3, morepreferred between 0.6 and 1.2, most preferred between 0.6 and 1.

The concentration of volatile organic compounds (VOC) in the aqueouscopolymer emulsions is preferably low. In a preferred case, the VOClevel is below 20 wt-%, more preferred below 10 wt-%, even morepreferred below 5 wt-%, most preferred below 1 wt-%, and even mostpreferred below 0.5 wt-%. Intentionally, the VOC level of the copolymeremulsions, prior to formulating them into paints, is close to 0 wt-%,typically below 0.1 wt-%.

When the copolymer composition is prepared via SAD polymerization,solvents are required for the solution polymerization process. Typicalsolvents include organic solvents that are well known to thoseexperienced in the field, such as acetone, methyl ethylketone, ethanol,methanol, i-propanol, i-octyl alcohol, xylene, glycol ethers, glycolesters. Preferably solvents are used that—following polymerization atelevated pressure—can be removed from the emulsion by evaporation.Preferred solvents in this respect are acetone and methyl ethylketone.

Initiators are required to start the radical polymerization. These, too,are well known to those experienced in the field. The aqueous emulsionpolymerisation can employ conventional free radical initiators such asperoxides, persulphates and redox systems. Useful examples includeinorganic peroxides, such as ammonium persulphate, sodium persulphate,potassium persulphate, AZO initiator, such as azobisisobutyronitrile(AIBN), 2,2′-azodi(2-methylbutyronitrile) (AMBN), and organic peroxideand hydroperoxides. (Hydro)peroxide can readily be used in combinationwith suitable reducing agents. Preferably, initiators are used in anamount of between 0.05 and 6%, more preferably between 0.5 and 4%, mostpreferably from 0.5 to 3% by weight of the total monomers.

Surfactants are used in emulsion polymerization as known to thoseskilled in the art. Typical surfactants have been extensively describedin all kinds of patent applications. The choice and concentration ofsurfactants are not deemed to be critical for this invention. Theaqueous emulsion polymerisation can be effected with conventionalemulsifying agents (surfactants) being used such as anionic and/ornon-ionic emulsifiers. The amount used is preferably low, preferably 0.3to 2% by weight, more usually 0.3 to 1% by weight based on the weight oftotal monomers charged to make the polymer.

In the case of SAD copolymer emulsions, emulsification can be aided byselecting the right anionic, nonionic and mixed anionic/nonionicsurfactant(s). Typically, surfactant is used in an amount of less than5% more preferably less than 3%, and most preferably between 0.2 and2.5% by weight of the total monomers.

Preferably (and subject to the provisos herein) in one embodiment of theinvention the process of making a copolymer emulsion of the inventioncomprises using a chaser monomer composition as described inWO2011073417. In another embodiment a chaser monomer may optionally notbe used.

In a preferred case the residual monomer content of the copolymeremulsion is below 2000 mg/L, more preferred below 1500 mg/L, mostpreferred below 1000 mg/L, and especially preferred below 550 mg/L.

The aqueous coating composition yields coatings with typical Könighardness values of at least 30 s, more preferred at least 40 s, evenmore preferred at least 50 s, and most preferred at least 60 s.

In another embodiment the polymer of the invention may be made using abulk polymerisation process. Bulk polymerisation of olefinicallyunsaturated monomers is described in detail in EP 0156170, WO82/02387,and U.S. Pat. No. 4,414,370 the contents of which are herebyincorporated by reference.

In general in a bulk polymerisation process a mixture of two or moremonomers are charged continuously into a reactor zone containing moltenvinyl polymer having the same ratio of vinyl monomers as the monomermixture. The molten mixture is maintained at a preset temperature toprovide a vinyl polymer of the desired molecular weight. The product ispumped out of the reaction zone at the same rates as the monomers arecharged to the reaction zone to provide a fixed level of vinyl monomerand vinyl polymer in the system. The particular flow rate selected willdepend upon the reaction temperature, vinyl monomers, desired molecularweight and desired polydispersity.

For polymers of the invention especially those to be used in coatingcompositions, providing amino functional groups thereon may also beuseful as such groups provide enhanced adhesion to certain substrates,such as wood and alkyd resins. Amino groups may be incorporated into apolymer by using a carboxyl functional precursor for example prepared byemploying ethylenically unsaturated acid functional monomer(s) such asacrylic acid or methacrylic acid. At least some of thecarboxy-functional groups may be converted to amino groups (as part ofamino ester groups) by reaction with alkylene imines such as ethyleneimine, propylene imine or butylene imine. Such a reaction is wellestablished in the art, being known as an imination reaction and thedetails of this are for example taught in U.S. Pat. No. 7,049,352 thecontents of which are hereby incorporated herein by reference. Thereforea further aspect of the invention comprises iminated versions of the allthe copolymers of the present invention as described herein.

If it is desired to crosslink polymers (for example in a polymerdispersion), the relevant polymers can carry functional groups such ashydroxyl groups and the dispersion subsequently formulated with acrosslinking agent such as a polyisocyanate, melamine, or glycoluril; orthe functional groups on one or both polymers could include keto oraldehyde carbonyl groups and the subsequently formulated crosslinker instep c) could be a polyamine or polyhydrazide such as adipic aciddihydrazide, oxalic acid dihydrazide, phthalic acid dihydrazide,terephthalic acid dihydrazide, isophorone diamine and4,7-dioxadecane-1,10 diamine. It will be noted that such crosslinkingagents will effect crosslinking by virtue of forming covalent bonds.

The designation of the polymer phase involved as a first phase or corematerial and second phase or shell material does not mean that theinvention should be bound by any particular morphology of the latexparticles. The term polymer phase is to be understood as meaning aportion of the emulsion polymer which is prepared during atemporally-limited segment of the emulsion polymerization and thedispersion of which differs from that of the foregoing or followingphase. This is also known as a multi-stage polymerization.

The two-phase structure of the dispersions of the invention influencesthe properties of the film formed when the dispersion dries aftercoating a substrate.

This aspect of the invention provides an aqueous vinyl polymerdispersion with an advantageous combination of MFFT and anti-blockingproperties which can be prepared at least in part from bio-renewablemonomers (such as biorenewable DBI).

According to this aspect of the present invention there is provided anaqueous polymer dispersion having a minimum film forming temperaturebelow 50° C., more preferably below 30° C. comprising a vinyl polymerderived from olefinically unsaturated monomers, with at least two phasescomprising:

-   -   A) 40 to 90 wt-%, more preferably 50 to 85 wt-% and especially        60 to 80 wt-% of a vinyl polymer A having a glass transition        temperature in the range of from −(minus)50 to 30° C.; and    -   B) 10 to 60 wt-%, more preferably 15 to 50 wt-% and especially        20 to 40 wt-% of a vinyl polymer B having a glass transition        temperature the range of from 50 to 130° C.; where        -   (i) at least one of the monomers used to prepare vinyl            polymer A and/or vinyl polymer B is represented by Formula 1            as described herein (usefully a higher itaconate ester such            as DBI) preferably in an amount from 20 to 80 wt-%, more            preferably from 20 to 65 wt-%, most preferably 30 to 55 wt-%            of the total monomers        -   (ii) optionally 10% by weight (preferably at least 20 wt-%)            of the total amount of monomer used to form vinyl polymer A            and vinyl polymer B is derived from at least one            bio-renewable olefinically unsaturated monomer;    -   where the weight percentage of monomers in A and B are        calculated in (i) and (ii) based on the total amount of        olefinically unsaturated monomers used to prepare polymer A and        polymer B being 100%;        -   (iii) vinyl polymer A comprises 0.1 to 10 wt-% of at least            one acid-functional olefinically unsaturated monomer where            the weight percentage of acid functional monomer is            calculated based on the total amount of olefinically            unsaturated monomer used to prepare polymer A being 100%.

In this aspect of the invention features (i) and (iii) correspondrespectively to components (a) and (b) of the present invention and theother monomers used to prepare polymers A and B corresponding tooptional components (c) and/or (d) as appropriate.

Other preferred features of this aspect of the present invention aregiven below and/or in the claims.

The acid-functional olefinically unsaturated monomer may be selectedfrom the group consisting of acrylic acid, methacrylic acid, itaconicanhydride, maleic anhydride methylene malonic acid, itaconic acid,crotonic acid and fumaric acid.

Vinyl polymer A may comprise 0.1 to 20 wt-% of at least one crosslinkingolefinically unsaturated monomer, preferably 0.4 to 6 wt-% of at leastone olefinically unsaturated monomer with a wet-adhesion promotingfunctionality.

The crosslinking monomer(s) and wet adhesion promoting monomer(s) can beused together in the same polymer composition. It is, however, oftendesired to use either crosslinking monomer(s) or wet adhesion promotingmonomer(s) in any phase. This means that vinyl polymer A can comprisecrosslinking monomer(s) or wet adhesion promoting monomer(s), whilevinyl polymer contains wet adhesion promoting monomer(s) or crosslinkingmonomer(s). In addition to this it is also possible to use wet adhesionpromoting monomer(s) in either vinyl polymer A and/or vinyl polymer B orin both and no crosslinking monomer(s) or to use crosslinking monomer(s)in vinyl polymer A and/or vinyl polymer B and no wet adhesion promotingmonomer(s).

Olefinically unsaturated monomer with a wet-adhesion promotingfunctionality contain wet-adhesion promoting functional groups such asacetoacetoxy groups and optionally substituted amine or urea groups, forexample cyclic ureido groups, imidazole groups, pyridine groups,hydrazine or semicarbazide groups.

The bio-renewable olefinically unsaturated monomers may comprisebio-renewable (meth)acrylic acid and or bio-renewable alkyl(meth)methacrylate.

The bio-renewable olefinically unsaturated monomers may also comprisebio-renewable: α-methylene butyrolactone, α-methylene valerolactone,α-methylene γ-R¹ butyrolactone (R¹ can be an optionally substitutedalkyl or optionally substituted aryl); itaconates such as dialkylitaconates and monoalkyl itaconates, itaconic acid, itaconic anhydride,crotonic acid and alkyl esters thereof, citraconic acid and alkyl estersthereof, methylene malonic acid and its mono and dialkyl esters,citraconic anhydride, mesaconic acid and alkyl esters thereof.

The bio-renewable monomers may also comprise bio-renewable: N—R²,α-methylene butyrolactam (R² can be an optionally substituted alkyl oroptionally substituted aryl); N—R², α-methylene γ-R¹ butyrolactam;N-alkyl itaconimids; itaconmonoamids; itacondiamids; dialkylitaconamides, mono alkyl itaconamides; furfuryl (meth)acrylate; andfatty acid functional (meth)acrylates.

Vinyl polymer A and vinyl polymer B may comprise at least about 1.5dpm/gC of carbon-14.

In a further aspect of the present invention provides a process forpreparing the aqueous polymer dispersion (or polymer A and polymer B asdescribed above)

which process comprises steps:

-   -   a) a first polymerization step, to form a first phase vinyl        polymer;    -   b) a second polymerization step in the presence of the resulting        first phase vinyl polymer from step a) to form a second phase        vinyl polymer.

Vinyl polymer A may be the first phase in which case vinyl polymer B isthe second phase. Alternatively vinyl polymer B may be the first phasein which case vinyl polymer A is the second phase. Preferably vinylpolymer A is the first phase. Preferably the second phase vinyl polymeris prepared in the presence of the first phase vinyl polymer.

Optionally the process includes c) a neutralisation step before/after orduring step c) to solubilise the first polymer phase.

Optionally the process includes d) the addition of a crosslinking agentafter the polymerization step a) and/or step b), said crosslinking agentbeing reactable with any crosslinking functional groups of vinyl polymerA and for vinyl polymer B on subsequent drying of the coating dispersionto effect covalent bond crosslinking.

Optionally the process includes a post treatment imination step e) withalkylene imines like for instance propylene imine) which can greatlyimprove wet adhesion.

A film, polish, varnish, lacquer, paint, ink and/or adhesive maycomprise the aqueous polymer dispersion comprising polymer A and polymerB described above and these aqueous polymer dispersions may also be usedprotective coatings on wood, plastic, paper and/or metal substrates.

An embodiment of the invention provides an aqueous polymer dispersionwhere vinyl polymers A and B comprise individually at least 30 wt-%,more preferably at least 40 wt-%, most preferably at least 60 wt-%, andespecially preferably at least 70 wt-% of compounds of Formula 1 such ashigher itaconate diesters for example DBI. Although the concentration ofitaconate monomers in polymers A and B can be similar, it is preferredthat the concentrations are different. In each of the preferred casesdescribed above, it is envisaged that the concentration of itaconatemonomers in the other phase can always be below 20 wt-% or even be 0wt-%.

Preferably the concentration of itaconate esters according to theinvention in the low Tg phase is at least 10 wt-% higher than that inthe high Tg phase, more preferably at least 20 wt-%.

In yet another preferred embodiment of the invention there is providedan aqueous polymer emulsion according to the invention where the monomerfeed making up polymer A or the feed making up polymer B comprise up to20 wt-% of organic solvent, more preferably less than 10 wt-%, even morepreferably less than 5 wt-%, and most preferably between 0.1 and 2.5wt-%.

Improved properties of the copolymers of the this aspect of theinvention may include heat resistance, colloidal stability, pigmentcompatibility, surface activity, blocking resistance and reduced MFFTdepending on the monomers used.

The monomer system used for the preparation of vinyl polymer A and vinylpolymer B is any suitable combination of olefinically unsaturatedmonomers which is amenable to copolymerisation (including bio-renewablemonomers described herein which may of course also be acid-functional,crosslinkable etc at described below).

Preferably vinyl polymer A comprises 0.5 to 9 wt-%, more preferably 1 to8 wt-% and especially 1.5 to 5 wt-% of at least one acid-functionalolefinically unsaturated monomer.

Preferably vinyl polymer B comprises less than 5 w % of any acidfunctional monomers and preferably less than 2 w %, and in somepreferred embodiments none at all.

Other, non-acid functional, non-crosslinking monomers which may becopolymerized with the acid monomers include acrylate and methacrylateesters and styrenes; also dienes such as 1,3-butadiene and isoprene,vinyl esters such as vinyl acetate, and vinyl alkanoates. Methacrylatesinclude normal or branched alkyl esters of C1 to C12 alcohols andmethacrylic acid, such as methyl methacrylate, ethyl methacrylate, andn-butyl methacrylate, and (usually C5 to C12) cycloalkyl methacrylatesacid such as isobornyl methacrylate and cyclohexyl methacrylate.Acrylates include normal and branched alkyl esters of C1 to C12 alcoholsand acrylic acid, such as methyl acrylate, ethyl acrylate, n-butylacrylate, and 2-ethylhexyl acrylate, and (usually C5-C12) cycloalkylacrylates such as isobornyl acrylate and cyclohexylacrylate. Alsoincluded are (meth)acrylamide, and mono- or di-alkyl amides of(meth)acrylic acid. Styrenes include styrene itself and the varioussubstituted styrenes, such as .alpha.-methyl styrene and t-butylstyrene. Nitriles such as acrylonitrile and methacrylonitrile may alsobe polymerised, as well as olefinically unsaturated halides such asvinyl chloride, vinylidene chloride and vinyl fluoride.

Functional monomers which impart crosslinkability (crosslinking monomersfor short) include epoxy (usually glycidyl) and hydroxyalkyl (usuallyC₁-C12, e.g. hydroxyethyl)methacrylates and acrylates, as well as ketoor aldehyde functional monomers such as acrolein, methacrolein and vinylmethyl ketone, the acetoacetoxy esters of hydroxyalkyl (usually C₁-C₁₂)acrylates and methacrylates such as acetoacetoxyethyl methacrylate andacrylate, and also keto-containing amides such as diacetone acrylamide.The purpose of using such functional monomer is to provide subsequentcrosslinkability in the resulting polymer system as discussed. Inprinciple the functional monomer used for imparting crosslinkabilitycould be acid-bearing monomer, but this is not usual.

Preferably vinyl polymer A comprises 0.1 to 3 wt-% of at least onecrosslinking monomer containing at least two olefinically unsaturatedgroups.

Preferably vinyl polymer A comprises 0.1 to 20 w %, preferably 1 to 15 w%, and particularly 1 to 10 w % of crosslinking monomers.

Adhesion promoting monomers include amino, urea, or N-heterocyclicgroups. As known to those skilled in the art this property can also beachieved by imination i.e. reaction of the acid groups with propyleneimine.

Preferably vinyl polymer A comprises 0.4 to 6 wt-% of at least oneolefinically unsaturated monomer with a wet-adhesion promotingfunctionality, more preferably between 0.5 and 4 wt-%.

Vinyl polymer A preferably has a weight average molecular weight (M_(w))as determined with GPC of from 20,000 to 6,000,000 g/mol, preferablymore than 80,000 g/mol and most preferably more than 100,000 g/mol. Morepreferably the upper limit does not exceed 4,000,000 g/mol.

Vinyl polymer B preferably has a weight average molecular weight (M_(w))as determined with GPC of from 20,000 to 6,000,000 g/mol, preferablymore than 80,000 g/mol and most preferably more than 100,000 g/mol. Morepreferably the upper limit does not exceed 4,000,000 g/mol.

Preferably vinyl polymer A has a glass transition temperature in therange of from −(minus)20 to 20° C.

Preferably vinyl polymer B has a glass transition temperature in therange of from 65 to 110° C.

Preferably the polymer dispersion contains latex particles having adiameter from 30 to 900 nanometres (nm), particularly 60 to 300 nm. Theparticle size distribution can be unimodal, bimodal, or polymodal.Dispersions having bi- or poly-modal particle size distributions can bemade according to the method described in DE3147 008 or U.S. Pat. No.4,456,726.

In a preferred embodiment there is provided an aqueous polymerdispersion having a minimum film forming temperature of below 30° C.comprising a vinyl polymer derived from olefinically unsaturatedmonomers, with at least two phases comprising:

-   -   A) 60 to 80 wt-% of a vinyl polymer A having a glass transition        temperature in the range of from −20 to 20° C.; and    -   B) 20 to 40 wt-% of a vinyl polymer B having a glass transition        temperature the range of from 65 to 110° C.;        wherein vinyl polymer A comprises 2 to 5 wt-% of at least one        acid-functional olefinically unsaturated monomer, and        wherein at least 50 wt-% of the monomer composition used to form        vinyl polymer A and vinyl polymer B comprises itaconate diesters        of Formula 1, preferably from a biorenewable source.

If vinyl polymer A is made in the second phase then preferably vinylpolymer A has at least 80%, more preferably at least 100% and mostpreferably 110% of the acid value of vinyl polymer B being made in thefirst phase and this helps to affect the morphology of the particles toget good film formation.

According to an embodiment of the invention there is also provided aprocess to obtain an aqueous polymer dispersion as defined herein whichprocess comprises steps:

-   -   a) a first polymerization step, to form a first phase vinyl        polymer;    -   b) a second polymerization step in the presence of the resulting        first phase vinyl polymer from step a) to form a second phase        vinyl polymer.

The first phase vinyl polymer may be formed using emulsionpolymerisation. Such processes are extremely well known, are describedelsewhere in this specification and need not be described further greatdetail.

If desired the pH of the polymer emulsion can be adjusted to highervalues using suitable bases. Examples of which include organic aminessuch as trialkylamines (e.g. triethylamine, tributylamine), morpholineand alkanolamines, and inorganic bases such as ammonia, NaOH, KOH, andLiOH.

In an embodiment of the invention it is also possible to use a gradientpolymerisation process as described in for example EP1434803 to make atleast part of the first and second phase. The second phase monomer feedpreferably starts after 20 to 80% completion of the first phase monomerfeed.

In a preferred embodiment when >30 wt-% of monomers of Formula 1 (suchas DBI) are used the monomers are preferably fed into the reactor duringpolymerisation, with a preferred feed time >60 minutes, morepreferably >120 minutes and most preferred >150 minutes.

Preferably, the concentration of unreacted monomer according to Formula1 during the polymerisation is less than 5 wt-% on total weight of theemulsion, more preferably less than 3 wt-%, most preferably less than 1wt-%, and typically less than 0.5 wt-% on total weight of the emulsion.The concentration of unreacted monomer(s) other than according toFormula 1 during the polymerisation is less than 5 wt-%, more preferredless than 2.5 wt-%, most preferably less than 1 wt-%, and typically lessthan 0.3 wt-% on total weight of the emulsion.

Preferably the dispersions of the invention have VOC levels of less than100 g/L and more preferably less than 80 g/L, most preferably less than50 g/L and especially less than 20 g/L of volatile organic components(VOC) such as coalescing solvents.

If crosslinking monomers are present then preferably the amount ofcrosslinking agent that is employed is such that the ratio of the numberof crosslinker groups present in the first phase vinyl polymer and (ifemployed) in the second phase vinyl polymer to the number of reactivegroups (for crosslinking purposes) in the crosslinking agent is withinthe range of from 10/1 to 1/3, preferably 2/1 to 1/1.5.

A crosslinker reactive with a copolymerised crosslinking monomer, ifpresent, is usually combined with the aqueous dispersion by adding itthereto after the preparation of the second phase vinyl polymer (andsometimes just before use of the dispersion), although it may inprinciple also be combined by performing the polymerisation of thesecond phase vinyl polymer in the presence of the crosslinking agent. Acombination of both incorporation expedients may also in principle beused.

It will be appreciated that vinyl polymer A and optionally vinyl polymerB possess functional groups for imparting latent crosslinkability to thedispersion (i.e. so that crosslinking takes place e.g. after theformation of a coating therefrom) when combined with the crosslinkingagent. For example, one or both polymers could carry functional groupssuch as hydroxyl groups and the dispersion subsequently formulated witha crosslinking agent such as a polyisocyanate, melamine, or glycoluril;or the functional groups on one or both polymers could include keto oraldehyde carbonyl groups and the subsequently formulated crosslinker instep c) could be a polyamine or polyhydrazide such as adipic aciddihydrazide, oxalic acid dihydrazide, phthalic acid dihydrazide,terephthalic acid dihydrazide, isophorone diamine and4,7-dioxadecane-1,10 diamine. It will be noted that such crosslinkingagents will effect crosslinking by virtue of forming covalent bonds.

According to an embodiment of the invention there is provided a processfor the production of the aqueous polymer coating dispersion, whichprocess comprises steps: a′) a first polymerization step, to form afirst phase vinyl polymer; b′) a second polymerization step in thepresence of the resulting first phase vinyl polymer from step a′) toform a second phase vinyl polymer. Optionally the process includes c′) aneutralisation step before/after or during step b′). Optionally theprocess includes a post treatment imination step d′) with alkyleneimines like for instance propylene imine) which can greatly improve wetadhesion. Optionally the process includes e′) the addition of acrosslinking agent after the polymerization step a′) and/or step b′),and preferably after the optional imination step d′), said crosslinkingagent being reactable with any crosslinking functional groups of vinylpolymer A and/or vinyl polymer B on subsequent drying of the coatingdispersion to effect covalent bond crosslinking (as described herein).

The term “activated unsaturated moiety”, is used herein to denote aspecies comprising at least one unsaturated carbon to carbon double bondin chemical proximity to at least one activating moiety. Preferably theactivating moiety comprises any group which activates an ethylenicallyunsaturated double bond for addition thereon by a suitableelectrophillic group. Conveniently the activating moiety comprises oxy,thio, (optionally organo substituted)amino, thiocarbonyl and/or carbonylgroups (the latter two groups optionally substituted by thio, oxy or(optionally organo substituted) amino). More convenient activatingmoieties are (thio)ether, (thio)ester and/or (thio)amide moiet(ies).Most convenient “activated unsaturated moieties” comprise an“unsaturated ester moiety” which denotes an organo species comprisingone or more “hydrocarbylidenyl(thio)carbonyl(thio)oxy” and/or one ormore “hydrocarbylidenyl(thio)-carbonyl(organo)amino” groups and/oranalogous and/or derived moieties for example moieties comprising(meth)acrylate functionalities and/or derivatives thereof. “Unsaturatedester moieties” may optionally comprise optionally substituted genericα,β-unsaturated acids, esters and/or other derivatives thereof includingthio derivatives and analogs thereof.

Preferred activated unsaturated moieties are those represented by aradical of Formula 4.

where n′ is 0 or 1, X⁶ is oxy or, thio; X⁷ is oxy, thio or NR¹⁷ (whereR¹⁷ represents H or optionally substituted organo), R¹³, R¹⁴, R¹⁵ andR¹⁶ each independently represent a bond to another moiety in Formula 1,H, optional substituent and/or optionally substituted organo groups,where optionally any of R¹³, R¹⁴, R¹⁵ and R¹⁶ may be linked to form aring; where at least one of R¹³, R¹⁴R¹⁵ and R¹⁶ is a bond; and allsuitable isomers thereof, combinations thereof on the same speciesand/or mixtures thereof.

The terms “activated unsaturated moiety”; “unsaturated ester moiety”and/or Formula 4 herein represents part of a formula herein and as usedherein these terms denote a radical moiety which depending where themoiety is located in the formula may be monovalent or multivalent (e.g.divalent).

More preferred moieties of Formula 4 (including isomers and mixturesthereof) are those where n′ is 1; X⁶ is O; X⁷ is O, S or NR⁷.

R¹³, R¹⁴, R¹⁵ and R¹⁶ are independently selected from: a bond, H,optional substituents and optionally substituted C₁₋₁₀hydrocarbo,optionally R¹⁵ and R¹⁶ may be linked to form (together with the moietiesto which they are attached) a ring; and where present R¹⁷ is selectedfrom H and optionally substituted C₁₋₁₀hydrocarbo.

Most preferably n′ is 1, X⁶ is O; X⁷ is O or S and R¹³R¹⁴, R¹⁵ and R¹⁶are independently a bond, H, hydroxy and/or optionally substitutedC₁₋₁₀hydrocarbyl.

For example n′ is 1, X⁶ and X⁷ are both O; and R³, R⁴, R⁵ and R⁶ areindependently a bond, H, OH, and/or C₁₋₄alkyl; or optionally R⁵ and R⁶may together form a divalent C₀₋₄alkylenecarbonylC₀₋₄alkylene moiety soFormula 4 represents a cyclic anhydride (e.g. when R¹⁵ and R¹⁶ togetherare carbonyl then Formula 4 represents a maleic anhydride or derivativethereof).

For moieties of Formula 4 where n′ is 1 and X⁶ and X⁷ are both O thenwhen one of (R¹³ and R¹⁴) is H and also R¹³ is H, Formula 4 representsan acrylate moiety, which includes acrylates (when both R¹³ and R¹⁴ areH) and derivatives thereof (when either R¹³ and R¹⁴ is not H). Similarlywhen one of (R¹³ and R¹⁴) is H and also R¹⁵ is CH₃, Formula 4 representsan methacrylate moiety, which includes methacrylates (when both R¹³ andR¹⁴ are H) and derivatives thereof (when either R¹³ and R¹⁴ is not H).Acrylate and/or methacrylate moieties of Formula 5 are particularlypreferred.

Conveniently moieties of Formula 4 are those where n′ is 1; X⁶ and X⁷are both O; R¹³ and R¹⁴ are independently a bond, H, CH₃ or OH, and R¹⁵is H or CH₃; R¹⁶ is H or R¹⁵ and R¹⁶ together are a divalent C═O group.

More conveniently moieties of Formula 4 are those where n′ is 1; X⁶ andX⁷ are both O; R¹³ is OH, R⁴ is CH₃, and R¹⁵ is H and R⁶ is a bondand/or tautomer(s) thereof (for example of an acetoacetoxy functionalspecies).

Most convenient unsaturated ester moieties are selected from:—OCO—CH═CH₂; —OCO—C(CH₃)═CH₂; acetoacetoxy, —OCOCH═C(CH₃)(OH) and allsuitable tautomer(s) thereof.

It will be appreciated that any suitable moieties represented by Formula4 could be used in the context of this invention such as other reactivemoieties.

Whilst the term vinyl polymer is commonly used to refer to thermoplasticpolymers derived by polymerization from compounds containing the vinylgroup (CH₂═CH—), the term “vinyl polymer” is used herein more broadly todenote any polymer (whether thermoplastic or not) that comprises (e.g.as repeat units therein) and/or is derived from monomers and/or polymerprecursors comprising one or more of the following moieties: activatedunsaturated moieties (such as acrylates and/or methacrylates); anyolefinically unsaturated moieties (such as vinyl moieties); mixturesthereof; and/or combinations thereof within the same moiety.

There is an increasing demand to use bio-renewable monomers in order toimprove the sustainability of the polymers used in for example coatingapplications. In view of concerns about depletion of fossil fuelresources or an increase in carbon dioxide in the air that poses aglobal-scale environmental problem in recent years, methods forproducing raw materials of these polymers from biomass resources haveattracted al lot of attention. Since these resources are renewable andtherefore have a carbon-neutral biomass, such methods are expected togain in particular importance in future. It is therefore a preferredfeature of the present invention and the aspects described herein thatwhere possible the monomers (especially the higher itaconate diesterssuch as DBI) as far as possible are biorenewable.

Preferably at least 30 wt-%, more preferably at least 50 wt-%, andespecially 70 wt-% of the olefinically unsaturated monomers used to formthe polymers of the invention are derived from at least onebio-renewable olefinically unsaturated monomer. Bio-renewable monomersmay be obtained fully or in part from bio-renewable sources. Thus it ispreferred to also measure the carbon-14 content to determine thebiorenewability.

The content of carbon-14 (C-14) is indicative of the age of a bio-basedmaterial. It is known in the art that C-14, which has a half life ofabout 5,700 years, is found in bio-renewable materials but not in fossilfuels. Thus, “bio-renewable materials” refer to organic materials inwhich the carbon comes from non-fossil biological sources. Examples ofbio-renewable materials include, but are not limited to, sugars,starches, corns, natural fibres, sugarcanes, beets, citrus fruits, woodyplants, cellulosics, lignocelluosics, hemicelluloses, potatoes, plantoils, other polysaccharides such as pectin, chitin, levan, and pullulan,and a combination thereof.

C-14 levels can be determined by measuring its decay process(disintegrations per minute per gram carbon or dpm/gC) through liquidscintillation counting. In one embodiment of the present invention,polymer A, polymer B and/or the olefinically unsaturated monomer(s) thatare used to obtain polymer A and/or polymer B may consideredsufficiently biorenewable for the purposes of this embodiment of theinvention when the respective polymer A, polymer B and/or olefinicallyunsaturated monomer comprise an amount of carbon-14 to produce a decayof at least about 1.5 dpm/gC (disintegrations per minute per gramcarbon), more preferably at least 2 dpm/gC, most preferably at least 2.5dpm/gC, and especially at least 4 dpm/gC.

It is preferred that the higher itaconate diesters such as DBI arebiorenewable, however other monomers used in the present invention mayalso be biorenewable. Examples of bio-renewable monomers include but arenot limited to bio-based acrylics obtained by for example usingbio-derived alcohols such as bio-butanol and include (meth)acrylic acidand alkyl (meth)acrylate, where alkyl is preferably selected frommethyl, ethyl, butyl or 2-ethylhexyl.

Acrylic acid can be made from glycerol, as is disclosed by Arkema, orfrom lactic acid as described by US7687661. Methacrylic acid can beprepared from ethene, methanol and carbon monoxide (all bio-renewable),as disclosed by Lucite International Ltd.

Olefinically unsaturated bio-renewable monomers which may additionallyprovide a contribution to improved coating properties includeα-methylene butyrolactone, α-methylene valerolactone, α-methylene γ-R³butyrolactone (R³ can be an optionally substituted alkyl or optionallysubstituted aryl); itaconates such as dialkyl itaconates (including DBI)and monoalkyl itaconates, itaconic acid, itaconic anhydride, crotonicacid and alkyl esters thereof, citraconic acid and alkyl esters thereof,methylene malonic acid and its mono and dialkyl esters, citraconicanhydride, mesaconic acid and alkyl esters thereof.

Other non-acid functional, non-crosslinking monomers include diesters ofitaconic acid. Preferred examples of such monomers include dimethylitaconate, diethyl itaconate, di-n-propyl itaconate, di-1-propylitaconate, di-n-butyl itaconate, di-1-butyl itaconate, and di-2-ethylhexyl itaconate.

Another useful set of useful bio-renewable monomers include N—R²,α-methylene butyrolactam (R² can be an optionally substituted alkyl oroptionally substituted aryl); N—R², α-methylene γ-R¹ butyrolactam;N-alkyl itaconimids; itaconmonoamids; itacondiamids; ialkylitaconamides, mono alkyl itaconamides; furfuryl (meth)acrylate; fattyacid functional (meth)acrylates such as DAPRO FX-522 from Elementis andVisiomer® MUMA from Evonik.

It is appreciated that certain features of the invention, which are forclarity described in the context of separate embodiments may also beprovided in combination in a single embodiment. Conversely variousfeatures of the invention, which are for brevity, described in thecontext of a single embodiment, may also be provided separately or inany suitable sub-combination.

The object of the present invention is to solve some or all of theproblems or disadvantages (such as identified throughout the applicationherein) with the prior art.

Unless the context clearly indicates otherwise, as used herein pluralforms of the terms herein are to be construed as including the singularform and vice versa.

The term “comprising” as used herein will be understood to mean that thelist following is non exhaustive and may or may not include any otheradditional suitable items, for example one or more further feature(s),component(s), ingredient(s) and/or substituent(s) as appropriate.

The terms ‘effective’, ‘acceptable’, ‘active’ and/or ‘suitable’ (forexample with reference to any process, use, method, application,preparation, product, material, formulation, compound, monomer,oligomer, polymer precursor, and/or polymers described herein asappropriate) will be understood to refer to those features of theinvention which if used in the correct manner provide the requiredproperties to that which they are added and/or incorporated to be ofutility as described herein. Such utility may be direct for examplewhere a material has the required properties for the aforementioned usesand/or indirect for example where a material has use as a syntheticintermediate and/or diagnostic tool in preparing other materials ofdirect utility. As used herein these terms also denote that a functionalgroup is compatible with producing effective, acceptable, active and/orsuitable end products.

Preferred utility of the present invention comprises as a coatingcomposition.

In the discussion of the invention herein, unless stated to thecontrary, the disclosure of alternative values for the upper and lowerlimit of the permitted range of a parameter coupled with an indicatedthat one of said values is more preferred than the other, is to beconstrued as an implied statement that each intermediate value of saidparameter, lying between the more preferred and less preferred of saidalternatives is itself preferred to said less preferred value and alsoto each less preferred value and said intermediate value.

For all upper and/or lower boundaries of any parameters given herein,the boundary value is included in the value for each parameter. It willalso be understood that all combinations of preferred and/orintermediate minimum and maximum boundary values of the parametersdescribed herein in various embodiments of the invention may also beused to define alternative ranges for each parameter for various otherembodiments and/or preferences of the invention whether or not thecombination of such values has been specifically disclosed herein. Thusfor example a substance stated as present herein in an amount from 0 to“x” (e.g. in units of mass and/or weight %) is meant (unless the contextclearly indicates otherwise) to encompass both of two alternatives,firstly a broader alternative that the substance may optionally not bepresent (when the amount is zero) or present only in an de-minimusamount below that can be detected. A second preferred alternative(denoted by a lower amount of zero in a range for amount of substance)indicates that the substance is present, and zero indicates that thelower amount is a very small trace amount for example any amountsufficient to be detected by suitable conventional analytical techniquesand more preferably zero denotes that the lower limit of amount ofsubstance is greater than or equal to 0.001 by weight % (calculated asdescribed herein).

It will be understood that the total sum of any quantities expressedherein as percentages cannot (allowing for rounding errors) exceed 100%.For example the sum of all components of which the composition of theinvention (or part(s) thereof) comprises may, when expressed as a weight(or other) percentage of the composition (or the same part(s) thereof),total 100% allowing for rounding errors.

However where a list of components is non exhaustive the sum of thepercentage for each of such components may be less than 100% to allow acertain percentage for additional amount(s) of any additionalcomponent(s) that may not be explicitly described herein.

In the present invention, unless the context clearly indicatesotherwise, an amount of an ingredient stated to be present in thecomposition of the invention when expressed as a weight percentage, iscalculated based on the total amount of monomers in the compositionbeing equivalent to 100% (thus for example components (a)+(b)+(c)+(d)total 100%). For convenience certain non monomer ingredients (such asfor example chain transfer agents (CTA)) which fall outside thedefinitions of any of components (a) to (d) may also be calculated asweight percentages based on total monomer (i.e. where the weight oftotal monomers alone is set at 100%). As the weight % of monomers (forexample for components (a) to (d)) by definition total 100% it will beseen that using monomer based weight % values for the non-monomeringredients (i.e. those components outside (a) to (d)) will mean thetotal percentages will exceed 100%. Thus amounts of non-monomeringredients expressed as monomer based weight percentages can beconsidered as providing a ratio for the weight amounts for theseingredients with respect to the total weight of monomers which is usedonly as a reference for calculation rather than as a strict percentage.Further ingredients are not excluded from the composition when(a)+(b)+(c)+(d) total 100% and weight percentages based on totalmonomers should not be confused with weight percentages of the totalcomposition.

The term “substantially” as used herein may refer to a quantity orentity to imply a large amount or proportion thereof. Where it isrelevant in the context in which it is used “substantially” can beunderstood to mean quantitatively (in relation to whatever quantity orentity to which it refers in the context of the description) therecomprises an proportion of at least 80%, preferably at least 85%, morepreferably at least 90%, most preferably at least 95%, especially atleast 98%, for example about 100% of the relevant whole. By analogy theterm “substantially-free” may similarly denote that quantity or entityto which it refers comprises no more than 20%, preferably no more than15%, more preferably no more than 10%, even more preferably no more than5%, most preferably no more than 2%, especially no more than 1.5%, forexample about 0% (e.g. completely absent or if present only in anundetectable amount) of the relevant whole.

The terms ‘optional substituent’ and/or ‘optionally substituted’ as usedherein (unless followed by a list of other substituents) signifies theone or more of following groups (or substitution by these groups):carboxy, sulpho, formyl, hydroxy, amino, imino, nitrilo, mercapto,cyano, nitro, methyl, methoxy and/or combinations thereof. Theseoptional groups include all chemically possible combinations in the samemoiety of a plurality (preferably two) of the aforementioned groups(e.g. amino and sulphonyl if directly attached to each other represent asulphamoyl group). Preferred optional substituents comprise: carboxy,sulpho, hydroxy, amino, mercapto, cyano, methyl, halo, trihalomethyland/or methoxy.

The synonymous terms ‘organic substituent’ and “organic group” as usedherein (also abbreviated herein to “organo”) denote any univalent ormultivalent moiety (optionally attached to one or more other moieties)which comprises one or more carbon atoms and optionally one or moreother heteroatoms. Organic groups may comprise organoheteryl groups(also known as organoelement groups) which comprise univalent groupscontaining carbon, which are thus organic, but which have their freevalence at an atom other than carbon (for example organothio groups).Organic groups may alternatively or additionally comprise organyl groupswhich comprise any organic substituent group, regardless of functionaltype, having one free valence at a carbon atom. Organic groups may alsocomprise heterocyclyl groups which comprise univalent groups formed byremoving a hydrogen atom from any ring atom of a heterocyclic compound:(a cyclic compound having as ring members atoms of at least twodifferent elements, in this case one being carbon). Preferably the noncarbon atoms in an organic group may be selected from: hydrogen, halo,phosphorus, nitrogen, oxygen, silicon and/or sulphur, more preferablyfrom hydrogen, nitrogen, oxygen, phosphorus and/or sulphur.

Most preferred organic groups comprise one or more of the followingcarbon containing moieties: alkyl, alkoxy, alkanoyl, carboxy, carbonyl,formyl and/or combinations thereof; optionally in combination with oneor more of the following heteroatom containing moieties: oxy, thio,sulphinyl, sulphonyl, amino, imino, nitrilo and/or combinations thereof.Organic groups include all chemically possible combinations in the samemoiety of a plurality (preferably two) of the aforementioned carboncontaining and/or heteroatom moieties (e.g. alkoxy and carbonyl ifdirectly attached to each other represent an alkoxycarbonyl group).

The term ‘hydrocarbo group’ as used herein is a sub-set of a organicgroup and denotes any univalent or multivalent moiety (optionallyattached to one or more other moieties) which consists of one or morehydrogen atoms and one or more carbon atoms and may comprise one or moresaturated, unsaturated and/or aromatic moieties. Hydrocarbo groups maycomprise one or more of the following groups. Hydrocarbyl groupscomprise univalent groups formed by removing a hydrogen atom from ahydrocarbon (for example alkyl). Hydrocarbylene groups comprise divalentgroups formed by removing two hydrogen atoms from a hydrocarbon, thefree valences of which are not engaged in a double bond (for examplealkylene). Hydrocarbylidene groups comprise divalent groups (which maybe represented by “R₂C═”) formed by removing two hydrogen atoms from thesame carbon atom of a hydrocarbon, the free valences of which areengaged in a double bond (for example alkylidene). Hydrocarbylidynegroups comprise trivalent groups (which may be represented by “RC≡”),formed by removing three hydrogen atoms from the same carbon atom of ahydrocarbon the free valences of which are engaged in a triple bond (forexample alkylidyne). Hydrocarbo groups may also comprise saturatedcarbon to carbon single bonds (e.g. in alkyl groups); unsaturated doubleand/or triple carbon to carbon bonds (e.g. in respectively alkenyl andalkynyl groups); aromatic groups (e.g. in aryl groups) and/orcombinations thereof within the same moiety and where indicated may besubstituted with other functional groups

The term ‘alkyl’ or its equivalent (e.g. ‘alk’) as used herein may bereadily replaced, where appropriate and unless the context clearlyindicates otherwise, by terms encompassing any other hydrocarbo groupsuch as those described herein (e.g. comprising double bonds, triplebonds, aromatic moieties (such as respectively alkenyl, alkynyl and/oraryl) and/or combinations thereof (e.g. aralkyl) as well as anymultivalent hydrocarbo species linking two or more moieties (such asbivalent hydrocarbylene radicals e.g. alkylene).

Any radical group or moiety mentioned herein (e.g. as a substituent) maybe a multivalent or a monovalent radical unless otherwise stated or thecontext clearly indicates otherwise (e.g. a bivalent hydrocarbylenemoiety linking two other moieties). However where indicated herein suchmonovalent or multivalent groups may still also comprise optionalsubstituents. A group which comprises a chain of three or more atomssignifies a group in which the chain wholly or in part may be linear,branched and/or form a ring (including spiro and/or fused rings). Thetotal number of certain atoms is specified for certain substituents forexample C_(1-N)organo, signifies a organo moiety comprising from 1 to Ncarbon atoms. In any of the formulae herein if one or more substituentsare not indicated as attached to any particular atom in a moiety (e.g.on a particular position along a chain and/or ring) the substituent mayreplace any H and/or may be located at any available position on themoiety which is chemically suitable and/or effective.

Preferably any of the organo groups listed herein comprise from 1 to 36carbon atoms, more preferably from 1 to 18. It is particularly preferredthat the number of carbon atoms in an organo group is from 1 to 12,especially from 1 to 10 inclusive, for example from 1 to 4 carbon atoms.

As used herein chemical terms (other than IUAPC names for specificallyidentified compounds) which comprise features which are given inparentheses—such as (alkyl)acrylate, (meth)acrylate and/or(co)polymer—denote that that part in parentheses is optional as thecontext dictates, so for example the term (meth)acrylate denotes bothmethacrylate and acrylate.

Certain moieties, species, groups, repeat units, compounds, oligomers,polymers, materials, mixtures, compositions and/or formulations whichcomprise and/or are used in some or all of the invention as describedherein may exist as one or more different forms such as any of those inthe following non exhaustive list: stereoisomers (such as enantiomers(e.g. E and/or Z forms), diastereoisomers and/or geometric isomers);tautomers (e.g. keto and/or enol forms), conformers, salts, zwitterions,complexes (such as chelates, clathrates, crown compounds,cyptands/cryptades, inclusion compounds, intercalation compounds,interstitial compounds, ligand complexes, organometallic complexes,non-stoichiometric complexes, π-adducts, solvates and/or hydrates);isotopically substituted forms, polymeric configurations [such as homoor copolymers, random, graft, comb and/or block polymers, linear and/orbranched polymers (e.g. hyperbranched, star and/or side branched),cross-linked and/or networked polymers, polymers obtainable from diand/or tri-valent repeat units, dendrimers, polymers of differenttacticity (e.g. isotactic, syndiotactic or atactic polymers)];polymorphs (such as interstitial forms, crystalline forms and/oramorphous forms), different phases, solid solutions; and/or combinationsthereof and/or mixtures thereof where possible. The present inventioncomprises and/or uses all such forms which are effective as definedherein.

Polymers of the present invention may be prepared by one or moresuitable polymer precursor(s) which may be organic and/or inorganic andcomprise any suitable (co)monomer(s), (co)polymer(s) [includinghomopolymer(s)] and mixtures thereof which comprise moieties which arecapable of forming a bond with the or each polymer precursor(s) toprovide chain extension and/or cross-linking with another of the or eachpolymer precursor(s) via direct bond(s) as indicated herein.

Polymer precursors of the invention may comprise one or more monomer(s),oligomer(s), polymer(s); mixtures thereof and/or combinations thereofwhich have suitable polymerisable functionality. It will be understoodthat unless the context dictates otherwise term monomer as used hereinencompasses the term polymer precursor and does not necessarily excludemonomers that may themselves be polymeric and/or oligomeric incharacter.

A monomer is a substantially monodisperse compound of a low molecularweight (for example less than one thousand daltons) which is capable ofbeing polymerised.

A polymer is a polydisperse mixture of macromolecules of large molecularweight (for example many thousands of daltons) prepared by apolymerisation method, where the macromolecules comprises the multiplerepetition of smaller units (which may themselves be monomers, oligomersand/or polymers) and where (unless properties are critically dependenton fine details of the molecular structure) the addition or removal oneor a few of the units has a negligible effect on the properties of themacromolecule.

A oligomer is a polydisperse mixture of molecules having an intermediatemolecular weight between a monomer and polymer, the molecules comprisinga small plurality of monomer units the removal of one or a few of whichwould significantly vary the properties of the molecule.

Depending on the context the term polymer may or may not encompassoligomer.

The polymer precursor of and/or used in the invention may be prepared bydirect synthesis or (if the polymeric precursor is itself polymeric) bypolymerisation. If a polymerisable polymer is itself used as a polymerprecursor of and/or used in the invention it is preferred that such apolymer precursor has a low polydispersity, more preferably issubstantially monodisperse, to minimise the side reactions, number ofby-products and/or polydispersity in any polymeric material formed fromthis polymer precursor. The polymer precursor(s) may be substantiallyun-reactive at normal temperatures and pressures.

Except where indicated herein polymers and/or polymeric polymerprecursors of and/or used in the invention can be (co)polymerised by anysuitable means of polymerisation well known to those skilled in the art.Examples of suitable methods comprise: thermal initiation; chemicalinitiation by adding suitable agents; catalysis; and/or initiation usingan optional initiator followed by irradiation, for example withelectromagnetic radiation (photo-chemical initiation) at a suitablewavelength such as UV; and/or with other types of radiation such aselectron beams, alpha particles, neutrons and/or other particles.

The substituents on the repeating unit of a polymer and/or oligomer maybe selected to improve the compatibility of the materials with thepolymers and/or resins in which they may be formulated and/orincorporated for the uses described herein. Thus the size and length ofthe substituents may be selected to optimise the physical entanglementor interlocation with the resin or they may or may not comprise otherreactive entities capable of chemically reacting and/or cross linkingwith such other resins as appropriate.

Another aspect of the invention broadly provides a coating compositioncomprising the polymers and/or beads of the present invention and/or asdescribed herein.

A further aspect of the invention provides a coating obtained orobtainable from a coating composition of the present invention.

A yet other aspect of the invention broadly provides a substrate and/orarticle having coated thereon an (optionally cured) coating compositionof the present invention.

A yet further aspect of the invention broadly provides a method of usingpolymers of the present invention and/or as described herein to preparea coating composition.

A still further aspect of the invention broadly provides a method forpreparing a coated substrate and/or article comprising the steps ofapplying a coating composition of the present invention to the substrateand/or article and optionally curing said composition in situ to form acured coating thereon. The curing may be by any suitable means, such asthermally, by radiation and/or by use of a cross-linker.

Preferred coating compositions are solvent coating compositions oraqueous coating compositions, more preferably are aqueous coatingcompositions.

Optionally aqueous coating compositions may also comprise a co-solvent.A co-solvent, as is well known in the coating art, is an organic solventemployed in an aqueous composition to ameliorate the dryingcharacteristics thereof, and in particular to lower its minimum filmforming temperature. The co-solvent may be solvent incorporated or usedduring preparation of polymers of the invention or may have been addedduring formulation of the aqueous composition.

The compositions of the invention are particularly useful as or forproviding the principle component of coating formulations (i.e.composition intended for application to a substrate without furthertreatment or additions thereto) such as protective or decorative coatingcompositions (for example paint, lacquer or varnish) wherein aninitially prepared composition optionally may be further diluted withwater and/or organic solvents, and/or combined with further ingredientsor may be in more concentrated form by optional evaporation of waterand/or organic components of the liquid medium of an initially preparedcomposition.

The compositions of the invention may be used in various applicationsand for such purposes may be optionally further combined or formulatedwith other additives and/or components, such as defoamers, rheologycontrol agents, thickeners, dispersing and/or stabilizing agents(usually surfactants and/or emulsifiers), wetting agents, fillers,extenders, fungicides, bacteriocides, coalescing and wetting solvents orco-solvents (although solvents are not normally required), plasticisers,anti-freeze agents, waxes, colorants, pigments, dyes, heat stabilisers,levelling agents, anti-cratering agents, fillers, sedimentationinhibitors, UV absorbers, antioxidants, reactive diluents, neutralisingagents, adhesion promoters and/or any suitable mixtures thereof.

The aforementioned additives and/or components and the like may beintroduced at any stage of the production process or subsequently. It ispossible to include fire retardants (such as antimony oxide) to enhancefire retardant properties.

The compositions of the invention may also be blended with otherpolymers such as vinyl polymers, alkyds (saturated or unsaturated),polyesters and or polyurethanes.

The coating composition of the invention may be applied to a variety ofsubstrates including wood, board, metals, stone, concrete, glass, cloth,leather, paper, plastics, foam and the like, by any conventional methodincluding brushing, dipping, flow coating, spraying, and the like. Thecoating composition of the invention may also be used to coat theinterior and/or exterior surfaces of three-dimensional articles. Thecoating compositions of the invention may also be used, appropriatelyformulated if necessary, for the provision of films, polishes,varnishes, lacquers, paints, inks and adhesives. However, they areparticularly useful and suitable for providing the basis of protectivecoatings for substrates that comprise wood (e.g. wooden floors),plastics, polymeric materials, paper and/or metal.

The carrier medium may be removed from the compositions of the inventiononce they have been applied to a substrate by being allowed to drynaturally at ambient temperature, or the drying process may beaccelerated by heat. Crosslinking can be developed by allowing to standfor a prolonged period at ambient temperature (several days) or byheating at an elevated temperature (e.g. 50° C.) for a much shorterperiod of time.

Many other variations embodiments of the invention will be apparent tothose skilled in the art and such variations are contemplated within thebroad scope of the present invention.

Further aspects of the invention and preferred features thereof aregiven in the claims herein.

Tests Minimum Film Forming Temperature

The minimum film forming temperature (MFFT) of a dispersion as usedherein is the temperature where the dispersion forms a smooth and crackfree coating or film using DIN 53787 and when applied using a Sheen MFFTbar SS3000.

Spot Tests

Coating films formed by blends of the invention can be tested in wellknown conventional spot tests (such as ASTM D1308-02e1) to determine theresistance of the film to various liquid reagents such as water,ethanol, detergent (e.g. that available commercially from Unilever underthe trade mark Andy) and coffee. In one such test a standard volume(e.g. 0.5 ml) of the liquid reagent may be applied to the film to form aspot thereon (e.g. by pipette) which is then covered with a watch glass.After the time specified (e.g. in the tables herein) the film can beassessed and rated visually on a scale of 1 to 5 as described below.

Koening Hardness

Koening hardness as used herein is a standard measure of hardness, beinga determination of how the viscoelastic properties of a film formed fromthe dispersion slows down a swinging motion deforming the surface of thefilm, and is measured according to DIN 53157 NEN5319.

Glass Transition Temperature (Tg)

As is well known, the glass transition temperature of a polymer is thetemperature at which it changes from a glassy, brittle state to aplastic, rubbery state. The glass transition temperatures may bedetermined experimentally using Differential Scanning calorimetry (DSC),taking the peak of the derivative curve as Tg, or calculated from theFox equation. Thus the Tg, in degrees Kelvin, of a copolymer having “n”copolymerised comonomers is given by the weight fractions W of eachcomonomer type and the Tgs of the homopolymers (in degrees Kelvin)derived from each comonomer according to the equation:

$\frac{1}{Tg} = {\frac{W_{1}}{{Tg}_{1}} + \frac{W_{2}}{{Tg}_{2}} + {\ldots \mspace{14mu} \frac{W_{n}}{{Tg}_{n}}}}$

The calculated Tg in degrees Kelvin may be readily converted to ° C.

Solids Content

The solids content of an aqueous dispersion of the invention is usuallywithin the range of from about 20 to 65 wt-% on a total weight basis,more usually 30 to 55 wt-%. Solids content can, if desired, be adjustedby adding water or removing water (e.g. by distillation orultrafiltration).

pH Value

The pH value of the dispersion of the invention can be from 2 to 10 andmostly is from 6 to 9.5.

Blocking Block Resistance Measurement [Includes Blocking and EarlyBlocking]: Step 1: Blocking:

A 100 micron wet film of the aqueous emulsion of the invention to which10% butyldiglycol is added is cast on to a paper substrate and dried for16 hours at 52° C.

Step 1: Early Blocking:

A 250 micron wet film of the aqueous emulsion of the invention to which10% butyldiglycol was added, is cast on to a paper substrate and driedfor 24 hours at room temperature.

Step 2: Blocking and Early Blocking:

After cooling down to room temperature two pieces of coated film areplaced with the coated side against each other under a load of 1Kg/cm.sup.2 for 4 hours at 52° C. After this time interval the load onthe samples is removed and the samples are left to cool down to roomtemperature (22+−2° C.). When the two coatings can be removed from eachother without any damage to the film (do not stick) the block resistanceis very good and assessed as a 5. When they however completely sticktogether, block resistance is very bad and assessed as a 0.

Gas Chromatography Mass Spectrometry (GCMS)

to confirm polymerisation is substantially complete the content of freeitaconate ester monomers content can be determined by GCMS. The GCMSanalyses were performed on a Trace GC-DSQ MS (Interscience, Breda, theNetherlands) equipped with a CTC combi Pal robotic autosampler for headspace has been used. The carrier gas was Helium and a CP Sil 5 lowbleed/MS, 25 m×0.25 mm i.d., 1.0 μm (CP nr. 7862) column has been used.

The GC-oven was programmed from 50° C. (5 min) followed by differentsequential temperature ramps of 5° C./min to 70° C. (0 min), 15° C./minto 220° C. (0 min), and ending with 25° C./min to 280° C. (10 min). Acontinuous Helium flow of 1.2 ml/min was used. A hot split injection at300° C. was performed on a programmed temperature vaporizer (PTV). Theinjection volume was 1 μl. The MS transfer line and ion source were bothkept at 250° C. The samples were measured with single ion monitoring(SIM). For the specific case of dibutyl itaconate (DBI) the masses 127.0and 59.0 Da were used, for the internal standard (iso butyl acrylate)the masses 55.0 and 73.0 were applied. The sample solutions wereapproximately 500 mg in 3 ml of internal standard solution (iso butylacrylate in acetone). The calibration was performed with 5 differentconcentration levels from 0 to 500 ppm. The calculation was performedusing Microsoft Excel with a linear calibration curve.

Molecular Weight

Unless the context clearly dictates otherwise the term molecular weightof a polymer or oligomer as used herein denotes weight average molecularweight (also denoted as M_(w)). M_(w) may be measured by any suitableconventional method for example by Gas Phase Chromatography(GPC—performed similarly to the GCMS method described above) and/or bythe SEC method described below. GPC method is preferred

Determination of Molecular Weight of a Polymer Using SEC

The molecular weight of a polymer may also be determined using SizeExclusion Chromatography (SEC) with tetrahydrofuran as the eluent orwith 1,1,1,3,3,3 hexafluoro isopropanol as the eluent.

1) Tetrahydrofuran

The SEC analyses were performed on an Alliance Separation Module (Waters2690), including a pump, auto injector, degasser, and column oven. Theeluent was tetrahydrofuran (THF) with the addition of 1.0 vol % aceticacid. The injection volume was 150 μl. The flow was established at 1.0ml/min. Three PL MixedB (Polymer Laboratories) with a guard column (3 μmPL) were applied at a temperature of 40° C. The detection was performedwith a differential refractive index detector (Waters 410). The samplesolutions were prepared with a concentration of 20 mg solids in 8 ml THF(+1 vol % acetic acid), and the samples were dissolved for a period of24 hours. Calibration is performed with eight polystyrene standards(polymer standard services), ranging from 500 to 4,000,000 g/mol. Thecalculation was performed with Millennium 32 software (Waters) with athird order calibration curve. The obtained molar masses are polystyreneequivalent molar masses (g/mol).

2) 1,1,1,3,3,3 Hexafluoro Isopropanol

The SEC analyses were performed on a Waters Alliance 2695 (pump,degasser and autosampler) with a Shodex RI-101 differential refractiveindex detector and Shimadzu CTO-20AC column oven. The eluent was1,1,1,3,3,3 hexafluoro isopropanol (HFIP) with the addition of 0.2Mpotassium trifluoro acetate (KTFA). The injection volume was 50 μl. Theflow was established at 0.8 ml/min. Two PSS PFG Linear XL columns(Polymer Standards Service) with a guard column (PFG PSS) were appliedat a temperature of 40° C. The detection was performed with adifferential refractive index detector. The sample solutions wereprepared with a concentration of 5 mg solids in 2 ml HFIP (+0.2M KTFA),and the samples were dissolved for a period of 24 hours. Calibration isperformed with eleven polymethyl methacrylate standards (polymerstandard services), ranging from 500 to 2,000,000 g/mol. The calculationwas performed with Empower Pro software (Waters) with a third ordercalibration curve. The molar mass distribution is obtained viaconventional calibration and the molar masses are polymethylmethacrylate equivalent molar masses (g/mol).

Standard Conditions

As used herein, unless the context indicates otherwise, standardconditions (e.g. for drying a film) means a relative humidity of 50%±5%,ambient temperature (which denotes herein a temperature of 23° C.±2°)and an air flow of ≦ (less than or equal to) 0.1 m/s.

The following examples are provided to further illustrate the processesand compositions of the present invention. These examples areillustrative only and are not intended to limit the scope of theinvention in any way. Unless otherwise specified all parts, percentages,and ratios are on a weight basis. The prefix C before an exampleindicates that it is comparative.

Various registered trademarks, other designations and/or abbreviationsare used herein to denote some of ingredients used to prepare polymersand compositions of the invention. These are identified below bychemical name and/or trade-name and optionally their manufacturer orsupplier from whom they are available commercially. However where achemical name and/or supplier of a material described herein is notgiven it may easily be found for example in reference literature wellknown to those skilled in the art: such as: ‘McCutcheon's Emulsifiersand Detergents’, Rock Road, Glen Rock, N.J. 07452-1700, USA, 1997 and/orHawley's Condensed Chemical Dictionary (14th Edition) by Lewis, RichardJ., Sr.; John Wiley & Sons.

In the examples the following abbreviations/monomers may be used:

BA=n-butyl acrylate (may be biorenewable)BMA=n-butyl methacrylate (may be prepared using bio-renewable alkanols)DBI denotes di(n-butyl) itaconate (also known as dibutyl2-methylidenebutanedioate) (may be bio-renewable)DDM denotes n-dodecyl mercaptaneDMI=dimethyl itaconate (may be bio-renewable)DMW denotes dematerialized waterEDTA=ethylene diamine tetraacetic acidHFIP denotes hexafluoro isopropanolKTFA denotes potassium trifluoro actetateMMA=methyl methacrylate (may be prepared using bio-renewable alkanols)MAA=methacrylic acid (may be biorenewable)NS denotes sodium sulfatePAA denotes polyacrylic acidSTY denotes styrene;D(iB)I denotes di(iso-butyl) itaconate (also known asdi(tert-butyl)itaconate)DPI denotes di(pentyl) itaconateDHI denotes di(hexyl) itaconateDHpI denotes di(heptyl) itaconateDOI denotes di(n-octyl) itaconateD(EH)I denotes di(2-ethylhexyl) itaconateDDI denotes di(decyl) itaconateDBzI denotes di(benzyl) itaconateDPhI denotes di(phenyl) itaconateBPI denotes butyl pentyl itaconateBHI denotes butyl hexyl itaconateHOI denotes hexyl n-octyl itaconateIA denotes itaconic acidMSA denotes the sulphonic acid of α-methyl styreneDPrI denotes di(propyl) itaconateCEA denotes beta carboxy ethyl acrylatePA denotes propyl acrylateOA denotes n-ocyl acrylateMBI denotes the mono acid butyl itaconate (i.e. half ester)IAn denotes itaconic anhydrideMMalA denotes methylene malonic acid,MalAn denotes maleic anhydride, iPHEMA denotes phosphated hydroxylethyl methacrylateAMPS denotes 2-acrylamido-2-methylpropane sulfonic acidURED denotes the monomer N-[2-(2-Oxo-1-imidazolidinyl)ethyl]methacrylateMSTY denotes alpha methyl styrene.

EXAMPLES 1 TO 3 Sequential Vinyl Polymers Example 1

To a round-bottomed flask equipped with a condenser, thermometer andmechanical stirrer 84.853 parts of water, 0.253 parts of sodiumbicarbonate, and 1.786 parts of a 30 wt-% solution of sodium laurylsulphate in water are added and this mixture is heated to 50° C. At 50°C., 10% of a first monomer feed consisting of 20.93 parts of water,4.285 of a 30 wt-% solution of sodium lauryl sulphate in water, 0.726parts of sodium bicarbonate, 0.246 parts of ammonium persulphate, 1.340parts of methacrylic acid, 26.811 parts of dibutyl itaconate, and 25.456parts of methyl methacrylate is added and the reactor contents areheated to 90° C. After the reaction temperature has been reached, thereactor contents are stirred for 15 minutes.

Next, the remainder of the first monomer feed is added over a period of210 minutes. When the feed is completed, the feed tank is rinsed with1.885 parts of water.

The batch is kept at 90° C. for 30 minutes and cooled the batch to 70°C. Next, a slurry comprising 0.289 parts of a 70 wt-% solution oft-butyl hydroperoxide in water and 1.228 parts of water is added and thebatch is stirred for 5 minutes. Next, a second monomer feed, comprising2.681 parts of methacrylic acid, 4.932 parts of methyl methacrylate,15.117 parts of butyl acrylate, and 30.877 parts of butyl methacrylateis added over a period of 240 minutes. Simultaneously, a catalyst feedcomprising 11.943 parts of water, 0.120 parts of i-ascorbic acid, and1.071 parts of a 30 wt-% solution of sodium lauryl sulphate, is fed overthe same period. After the second monomer feed is finished, the feedtank is rinsed with 1.885 parts of water.

The reactor contents are stirred at 70° C. for another 30 minutes, afterwhich the batch is cooled to 30° C. The pH of the emulsion is adjustedto 7 using 0.6 parts of a 25% solution of ammonia in water or part ofit. Simultaneously, 0.623 parts of water are added. The solids contentof the emulsion is adjusted to 45% using water.

The resulting emulsion has a solids content of 45%, and a pH of 7.0.

Example 2

To a round-bottomed flask equipped with a condenser, thermometer andmechanical stirrer 84.853 parts of water, 0.253 parts of sodiumbicarbonate, and 1.786 parts of a 30 wt-% solution of sodium laurylsulphate in water are added and this mixture is heated to 50° C. At 50°C., 10% of a first monomer feed consisting of 20.93 parts of water,4.285 of a 30 wt-% solution of sodium lauryl sulphate in water, 0.726parts of sodium bicarbonate, 0.246 parts of ammonium persulphate, 1.340parts of methacrylic acid, 14.044 parts of butyl methacrylate, 24.123parts of dimethyl itaconate, and 14.100 parts of methyl methacrylate isadded and the reactor contents are heated to 90° C. After the reactiontemperature has been reached, the reactor contents are stirred for 15minutes.

Next, the remainder of the first monomer feed is added over a period of210 minutes. When the feed is completed, the feed tank is rinsed with1.885 parts of water.

The batch is kept at 90° C. for 30 minutes and cooled the batch to 70°C. Next, a slurry comprising 0.289 parts of a 70 wt-% solution oft-butyl hydroperoxide in water and 1.228 parts of water is added and thebatch is stirred for 5 minutes. Next, a second monomer feed, comprising2.681 parts of methacrylic acid, 4.932 parts of methyl methacrylate,15.117 parts of butyl acrylate, 18.762 parts of dibutyl itaconate, and12.115 parts of butyl methacrylate is added over a period of 240minutes. Simultaneously, a catalyst feed comprising 11.943 parts ofwater, 0.120 parts of i-ascorbic acid, and 1.071 parts of a 30 wt-%solution of sodium lauryl sulphate, is fed over the same period. Afterthe second monomer feed is finished, the feed tank is rinsed with 1.885parts of water.

The reactor contents are stirred at 70° C. for another 30 minutes, afterwhich the batch is cooled to 30° C. The pH of the emulsion is adjustedto 7 using 0.6 parts of a 25% solution of ammonia in water or part ofit. Simultaneously, 0.623 parts of water are added. The solids contentof the emulsion is adjusted to 45% using water.

The resulting emulsion has a solids content of 45%, and a pH of 7.0.

Example 3

To a round-bottomed flask equipped with a condenser, thermometer andmechanical stirrer 84.853 parts of water, 0.253 parts of sodiumbicarbonate, and 1.786 parts of a 30 wt-% solution of sodium laurylsulphate in water are added and this mixture is heated to 50° C. At 50°C., 10% of a first monomer feed consisting of 20.93 parts of water,4.285 of a 30 wt-% solution of sodium lauryl sulphate in water, 0.726parts of sodium bicarbonate, 0.246 parts of ammonium persulphate, 1.340parts of methacrylic acid, 14.044 parts of butyl methacrylate, and38.223 parts of methyl methacrylate is added and the reactor contentsare heated to 90° C. After the reaction temperature has been reached,the reactor contents are stirred for 15 minutes.

Next, the remainder of the first monomer feed is added over a period of210 minutes. When the feed is completed, the feed tank is rinsed with1.885 parts of water.

The batch is kept at 90° C. for 30 minutes and cooled the batch to 70°C. Next, a slurry comprising 0.289 parts of a 70 wt-% solution oft-butyl hydroperoxide in water and 1.228 parts of water is added and thebatch is stirred for 5 minutes. Next, a second monomer feed, comprising2.681 parts of methacrylic acid, 4.932 parts of methyl methacrylate,2.673 parts of diacetone acrylamide, 12.444 parts of butyl acrylate,26.803 parts of dibutyl itaconate, and 4.074 parts of butyl methacrylateis added over a period of 240 minutes. Simultaneously, a catalyst feedcomprising 11.943 parts of water, 0.120 parts of i-ascorbic acid, and1.071 parts of a 30 wt-% solution of sodium lauryl sulphate, is fed overthe same period. After the second monomer feed is finished, the feedtank is rinsed with 1.885 parts of water.

The reactor contents are stirred at 70° C. for another 30 minutes, afterwhich the batch is cooled to 30° C. The pH of the emulsion is adjustedto 7 using 0.6 parts of a 25% solution of ammonia in water or part ofit. Simultaneously, 0.623 parts of water are added. The solids contentof the emulsion is adjusted to 45% using water.

The resulting emulsion has a solids content of 45%, and a pH of 7.0.

FURTHER EXAMPLES Examples 4 to 13

Further examples for the various embodiments can be prepared accordingthe Common method E below and with reference to the Table 1 below. Thepercentages in the tables are mostly quoted to the nearest percentageand/or to 2 significant figures and thus may not total 100% due torounding errors.

Common Method E (for Sequential Vinyl Polymers)

The total weight of monomer used in Examples below can be the same asthe total amount used to prepare Example 1 and so for convenience theamount of monomers used in these examples can be expressed as a weightpercent of the total monomers used in both the first and second monomerfeeds. The first monomer feed (used to prepare the low Tg part of thepolymer) consists of the same ingredients described in Example 1 (orwith consequent modification), other than the monomers which can be:z1%of Monomer Z1, y1% of Monomer Y1, x1% of Monomer X1 and/or w1% ofMonomer W1. To the equipment described in Example 1 and the pre-feeddescribed therein the same initial amount of the first monomer feed canbe added under the conditions described therein and then the remainderof the first monomer feed can be added and the reaction continued asdescribed in Example 1 (or with consequent modification) until thesecond monomer feed can be added. The second monomer feed (used toprepare the high Tg part of the polymer) consists of the sameingredients described in Example 1 (or with consequent modification),other than the monomers which can be:z2% of Monomer Z2, y2% of MonomerY2, x2% of Monomer X2 and/or w2% of Monomer W2.

The rest of the process can be followed as described in Example 1 (orwith consequent modification) with reference to Table 1 to obtain vinylsequential polymers analogous to that described in Example 1. Therelative weight ratio (R) of the respective total amount of low Tgpolymer A to the total amount of high Tg polymer B is also given inTable 2 and if necessary the method described in Example 1 can bemodified according by adjusting the weight of the total amount ofmonomers used to prepare polymer B relative to the weight of the totalamount of monomers used to prepare polymer A.

The total amount of monomer of Formula 1 (as a percentage T of the totalamount of monomers A+B is also given in Table 1)

TABLE 1 Examples 4 to 13 - sequential polymers (see method E) T % Low Tgpolymer A (% of A) High Tg polymer B (% of B) R (of Ex z1% Z1 y1% Y1 x1%X1 W1% W1 z2% Z2 y2 % Y2 x2% X2 w2% W2 (A to B) A + B) 4 10 MAA 40 MMA50 DPI — — 5 MAA 10 MMA 30 DMI 55 BMA 40/60 20 5 0.1 AA 39.9 MA 60 DHI —— 10 MAA 10 MMA 20 DEI 60 BMA 45/55 27 6 0.5 MSA 20 EA 65 DOI 14.5 BA 15MA 5 EMA 50 DPrI 30 OA 50/50 23.5 7 1 CEA 36 PA 30 DBI 33 MA 60 DBzI 30BA 10 DEI — — 55/45 43.5 8 2 MBI 80 MMA 18 EMA — — 85 DPhI 10 EMA  5 DMI— — 60/40 34 9 4 IA 22 BA 74 DBI — — 90 DHI 10 URED — — — — 65/35 79.610 6 IAn 20 MMA 64 DBI 10 EA 5 MAA 10 BA 65 DMI 20 BA 70/30 44.8 11 7.5MMaIA 40 EMA 52.5 BPI — — 10 AA 40 EHA 10 DEI 40 BMA 75/25 39.4 12 8PHEMA 30 MMA 42 BHI 20 EA 1 MMA 49 OA 50 DMI 80/20 33.6 13 3 AMPS 35 PA62 HOI — — 2 MSA 30 DBI 30 DEI 38 EA 90/10 58.8

Examples 14 to 18 and Comparative Examples Comp I to V Example 14 DBIPolymer Containing Wet-Adhesion Promoting Monomer

To a round-bottomed flask equipped with a condenser, thermometer, and astirrer were charged 559.2 parts of demineralized water, 5.5 parts ofsodium bicarbonate, 29.4 parts of a 30 wt-% solution of sodium laurylsulphate in water, and 1.1 parts of sodium persulphate. The reactorcontents were heated to 70° C. At 50° C., 10% of a monomer feedconsisting of 510.3 parts of demineralized water, 12.5 parts of a 30wt-% solution of sodium lauryl sulphate in water, 516.7 parts of butylacrylate, 33.0 parts of methacrylic acid, 494.7 parts of dibutylitaconate, and 110.0 parts of a 50 wt-% solution ofN-(2-methacryloyloxyethyl)ethylene urea in water (Plex 6852-0, ex.Evonik), was added. Due to the exothermic nature of the polymerizingmonomers, the temperature increased to 85° C. (if the exotherm would beinsufficient the mixture could be heated slightly to reach a temperatureof 85° C.). At 85° C., the monomer feed, comprising the remaining 90% ofthe original feed, and the initiator feed, consisting of 124.5 parts ofdemineralized water, 4.4 parts of sodium persulphate, and 2.2 parts of a30 wt-% solution of sodium lauryl sulphate in water, were started. Bothfeeds were added over a period of 120 minutes. At the end of the monomerfeed, the feed tank was rinsed with 19.7 parts of demineralized waterand the mixture was stirred at 85° C. for another 35 minutes.

Next, the emulsion was cooled to 45° C., and a solution of 0.7 parts ofiso-ascorbic acid in 12.5 parts of demineralized water was added,followed by 1.0 part of a 70 wt-% solution of t-butyl hydroperoxide inwater, 1.5 parts of demineralized water, and 0.3 parts of a 30 wt-%solution of sodium lauryl sulphate in water. The entire reactor contentswere stirred for 30 minutes at 45° C.

The emulsion was cooled to room temperature, and 55.0 parts of an equalmixture of a 25% solution of ammonia in water and demineralized waterwere added. The solids content of the emulsion was adjusted to 45% usingdemineralized water.

Example 15 DBI and Styrene Containing Polymer

To a round-bottomed flask equipped with a condenser, thermometer, and astirrer were charged 644.0 parts of demineralized water, 0.5 parts ofsodium bicarbonate, 13.3 parts of a 30 wt-% solution of sodium laurylsulphate in water, and 0.8 parts of sodium persulphate. The reactorcontents were heated to 80° C. and stirred for 5 minutes at 80° C. Next,10% of a monomer feed, consisting of 132.9 parts of demineralized water,13.0 parts of a 30 wt-% solution of sodium lauryl sulphate in water,23.3 parts of methacrylic acid, 280.1 parts of dibutyl itaconate, and280.1 parts of styrene, was added, after the temperature rose toapproximately 90° C. due to the exothermic nature of the polymerization.As soon as the temperature of 90° C. was reached, the remaining monomerfeed and the initiator feed, consisting of 58.7 parts of demineralizedwater, 2.5 parts of sodium persulphate, and 3.7 parts of a 30 wt-%solution of sodium lauryl sulphate in water, were started. Both feedswere added over a period of 2 hours. At the end of the monomer feed thefeed tank was rinsed with 10.4 parts of demineralized water. Thetemperature of the reactor contents were cooled to 80° C., after which asolution of 1.8 parts of iso-ascorbic acid dissolved in 26.5 parts ofdemineralized water (which was brought to a pH of 8.5 using an ammoniasolution) was fed over a period of 30 minutes, during which a mixture of2.8 parts of t-butyl hydroperoxide and 5.6 parts of demineralized waterwas added in two shots; one at the start of the iso-ascorbic acid feedand 15 minutes later.

At the end of the feed, the mixture was stirred at 80° C. for 30minutes, and the pH was raised to 7.2 using a 25 wt-% solution ofammonia in water. After stirring for another 30 minutes, the batch wascooled to room temperature. The solids content was adjusted to 40% usingdemineralized water.

Comparative Example Comp I BA and Styrene Containing Polymer

To a round-bottomed flask equipped with a condenser, thermometer, and astirrer were charged 639.5 parts of demineralized water, 0.5 parts ofsodium bicarbonate, and 13.3 parts of a 30 wt-% solution of sodiumlauryl sulphate in water. The reactor contents were heated to 80° C.,after which a solution of 0.8 parts of sodium persulphate in 4.5 partsof demineralized water were added and stirred for 5 minutes at 80° C.Next, 10% of a monomer feed, consisting of 132.9 parts of demineralizedwater, 13.0 parts of a 30 wt-% solution of sodium lauryl sulphate inwater, 23.3 parts of methacrylic acid, 280.1 parts of butyl acrylate,and 280.1 parts of styrene, was added, after the temperature rose toapproximately 90° C. due to the exothermic nature of the polymerization.As soon as the temperature of 90° C. was reached, the remaining monomerfeed and the initiator feed, consisting of 58.7 parts of demineralizedwater, 2.5 parts of sodium persulphate, and 3.7 parts of a 30 wt-%solution of sodium lauryl sulphate in water, were started. Both feedswere added over a period of 2 hours. At the end of the monomer feed thefeed tank was rinsed with 10.4 parts of demineralized water. Thetemperature of the reactor contents were cooled to 80° C., after which asolution of 1.8 parts of iso-ascorbic acid dissolved in 26.5 parts ofdemineralized water (which was brought to a pH of 8.5 using an ammoniasolution) was fed over a period of 30 minutes, during which a mixture of2.8 parts of t-butyl hydroperoxide and 5.6 parts of demineralized waterwas added in two shots; one at the start of the iso-ascorbic acid feedand 15 minutes later.

At the end of the feed, the mixture was stirred at 80° C. for 30minutes, and the pH was raised to 7.2 using a 25 wt-% solution ofammonia in water. After stirring for another 30 minutes, the batch wascooled to room temperature. The solids content was adjusted to 40% usingdemineralized water.

Example 16 DBI and MMA Containing Polymer

To a round-bottomed flask equipped with a condenser, thermometer, and astirrer were charged 639.5 parts of demineralized water, 0.5 parts ofsodium bicarbonate, and 13.3 parts of a 30 wt-% solution of sodiumlauryl sulphate in water. The reactor contents were heated to 80° C.,after which a solution of 0.8 parts of sodium persulphate in 4.5 partsof demineralized water were added and stirred for 5 minutes at 80° C.Next, 10% of a monomer feed, consisting of 132.9 parts of demineralizedwater, 13.0 parts of a 30 wt-% solution of sodium lauryl sulphate inwater, 23.3 parts of methacrylic acid, 280.1 parts of dibutyl itaconate,and 280.1 parts of methyl methacrylate, was added, after the temperaturerose to approximately 90° C. due to the exothermic nature of thepolymerization. As soon as the temperature of 90° C. was reached, theremaining monomer feed and the initiator feed, consisting of 58.7 partsof demineralized water, 2.5 parts of sodium persulphate, and 3.7 partsof a 30 wt-% solution of sodium lauryl sulphate in water, were started.Both feeds were added over a period of 2 hours. At the end of themonomer feed the feed tank was rinsed with 10.4 parts of demineralizedwater. The temperature of the reactor contents were cooled to 80° C.,after which a solution of 1.8 parts of iso-ascorbic acid dissolved in26.5 parts of demineralized water (which was brought to a pH of 8.5using an ammonia solution) was fed over a period of 30 minutes, duringwhich a mixture of 2.8 parts of t-butyl hydroperoxide and 5.6 parts ofdemineralized water was added in two shots; one at the start of theiso-ascorbic acid feed and 15 minutes later.

At the end of the feed, the mixture was stirred at 80° C. for 30minutes, and the pH was raised to 7.2 using a 25 wt-% solution ofammonia in water. After stirring for another 30 minutes, the batch wascooled to room temperature. The solids content was adjusted to 40% usingdemineralized water.

Comparative Example Comp II BA and MMA Containing Polymer

To a round-bottomed flask equipped with a condenser, thermometer, and astirrer were charged 639.5 parts of demineralized water, 0.5 parts ofsodium bicarbonate, and 13.3 parts of a 30 wt-% solution of sodiumlauryl sulphate in water. The reactor contents were heated to 80° C.,after which a solution of 0.8 parts of sodium persulphate in 4.5 partsof demineralized water were added and stirred for 5 minutes at 80° C.Next, 10% of a monomer feed, consisting of 132.9 parts of demineralizedwater, 13.0 parts of a 30 wt-% solution of sodium lauryl sulphate inwater, 23.3 parts of methacrylic acid, 280.1 parts of butyl acrylate,and 280.1 parts of methyl methacrylate, was added, after the temperaturerose to approximately 90° C. due to the exothermic nature of thepolymerization. As soon as the temperature of 90° C. was reached, theremaining monomer feed and the initiator feed, consisting of 58.7 partsof demineralized water, 2.5 parts of sodium persulphate, and 3.7 partsof a 30 wt-% solution of sodium lauryl sulphate in water, were started.Both feeds were added over a period of 2 hours. At the end of themonomer feed the feed tank was rinsed with 10.4 parts of demineralizedwater. The temperature of the reactor contents were cooled to 80° C.,after which a solution of 1.8 parts of iso-ascorbic acid dissolved in26.5 parts of demineralized water (which was brought to a pH of 8.5using an ammonia solution) was fed over a period of 30 minutes, duringwhich a mixture of 2.8 parts of t-butyl hydroperoxide and 5.6 parts ofdemineralized water was added in two shots; one at the start of theiso-ascorbic acid feed and 15 minutes later.

At the end of the feed, the mixture was stirred at 80° C. for 30minutes, and the pH was raised to 7.2 using a 25 wt-% solution ofammonia in water. After stirring for another 30 minutes, the batch wascooled to room temperature. The solids content was adjusted to 40% usingdemineralized water.

Comparative Example Comp III DMI Containing Copolymer

To a round-bottomed flask equipped with a condenser, thermometer, and astirrer were charged 639.5 parts of demineralized water, 0.5 parts ofsodium bicarbonate, and 13.3 parts of a 30 wt-% solution of sodiumlauryl sulphate in water. The reactor contents were heated to 80° C.,after which a solution of 0.8 parts of sodium persulphate in 4.5 partsof demineralized water were added and stirred for 5 minutes at 80° C.Next, 10% of a monomer feed, consisting of 132.9 parts of demineralizedwater, 13.0 parts of a 30 wt-% solution of sodium lauryl sulphate inwater, 23.3 parts of methacrylic acid, 414.3 parts of dimethylitaconate, and 145.9 parts of ethyl acrylate, was added, after thetemperature rose to approximately 90° C. due to the exothermic nature ofthe polymerization. As soon as the temperature of 90° C. was reached,the remaining monomer feed and the initiator feed, consisting of 58.7parts of demineralized water, 2.5 parts of sodium persulphate, and 3.7parts of a 30 wt-% solution of sodium lauryl sulphate in water, werestarted. Both feeds should be added over a period of 2 hours.

After 110 minutes of the monomer feed, the emulsion gelled, showing thathigher itaconates, such as DBI, yield superior properties over loweritaconates, such as DMI.

Example 17 DBI Containing h/s Sequential Copolymer

To a round-bottomed flask equipped with a condenser, thermometer, and astirrer were charged 426.6 parts of demineralized water, 0.4 parts ofsodium bicarbonate, 31.3 parts of a 20 wt-% aqueous solution of aphosphate functional surfactant (Fosfodet FAZ109V, ex. KAO), and 0.4parts of a 25 wt-% ammonia solution. The reactor contents were heated to80° C., after which a solution of 0.4 parts of sodium persulphate in 7.9parts of demineralized water were added, followed by 10% of a firstmonomer feed consisting of 115.1 parts of demineralized water, 35.9parts of a 20 wt-% aqueous solution of a phosphate functional surfactant(Fosfodet FAZ109V, ex. KAO), 0.6 parts of sodium bicarbonate, 15.7 partsof acrylic acid, 90.1 parts of dibutyl itaconate, and 286.0 parts ofmethyl methacrylate. Due to the heat formed as a result of thepolymerizing monomers, the temperature rose to 90° C., after whichadding the remainder of the first monomer feed was started. The firstmonomer feed was added over a period of 45 minutes. Simultaneously, 60%of an initiator feed, consisting of 36.3 parts of demineralized water,0.2 parts of sodium bicarbonate, and 2.0 parts of sodium persulphate,was fed over a period of 45 minutes. At the end of the monomer feed, thefeed tank was rinsed with 7.6 parts of demineralized water.

Next, a mixture of 0.9 parts of a 25 wt-% ammonia solution and 1.2 partsof demineralized water was fed over a period of 15 minutes. 45 minutesafter the end of the first monomer feed, a second monomer feed,consisting of 76.7 parts of demineralized water, 23.9 parts of a 20 wt-%aqueous solution of a phosphate functional surfactant (Fosfodet FAZ109V,ex. KAO), 0.4 parts of sodium bicarbonate, 10.5 parts of acrylic acid,198.5 parts of dibutyl itaconate, and 52.2 parts of butyl acrylate, wasstarted. This feed, and the remainder of the initiator feed that was fedsimultaneously, were added over a period of 30 minutes. After completionof the second monomer feed, the feed tank was rinsed with 15.3 parts ofdemineralized water and the mixture was allowed to stir at 90° C. foranother 30 minutes.

Finally, the emulsion was cooled to room temperature, the solids contentwas corrected to 45% using demineralized water, and the pH was correctedto 7.5 using a 25 wt-% ammonia solution.

Comparative Example Comp IV DBI Free h/s Sequential Copolymer

To a round-bottomed flask equipped with a condenser, thermometer, and astirrer were charged 426.6 parts of demineralized water, 0.4 parts ofsodium bicarbonate, 31.3 parts of a 20 wt-% aqueous solution of aphosphate functional surfactant (Fosfodet FAZ109V, ex. KAO), and 0.4parts of a 25 wt-% ammonia solution. The reactor contents were heated to80° C., after which a solution of 0.4 parts of sodium persulphate in 7.9parts of demineralized water were added, followed by 10% of a firstmonomer feed consisting of 115.1 parts of demineralized water, 35.9parts of a 20 wt-% aqueous solution of a phosphate functional surfactant(Fosfodet FAZ109V, ex. KAO), 0.6 parts of sodium bicarbonate, 15.7 partsof acrylic acid, 90.1 parts of butyl acrylate, and 286.0 parts of methylmethacrylate. Due to the heat formed as a result of the polymerizingmonomers, the temperature rose to 90° C., after which adding theremainder of the first monomer feed was started. The first monomer feedwas added over a period of 45 minutes. Simultaneously, 60% of aninitiator feed, consisting of 36.3 parts of demineralized water, 0.2parts of sodium bicarbonate, and 2.0 parts of sodium persulphate, wasfed over a period of 45 minutes. At the end of the monomer feed, thefeed tank was rinsed with 7.6 parts of demineralized water.

Next, a mixture of 0.9 parts of a 25 wt-% ammonia solution and 1.2 partsof demineralized water was fed over a period of 15 minutes. 45 minutesafter the end of the first monomer feed, a second monomer feed,consisting of 76.7 parts of demineralized water, 23.9 parts of a 20 wt-%aqueous solution of a phosphate functional surfactant (Fosfodet FAZ109V,ex. KAO), 0.4 parts of sodium bicarbonate, 10.5 parts of acrylic acid,and 250.7 parts of butyl acrylate, was started. This feed, and theremainder of the initiator feed that was fed simultaneously, were addedover a period of 30 minutes. After completion of the second monomerfeed, the feed tank was rinsed with 15.3 parts of demineralized waterand the mixture was allowed to stir at 90° C. for another 30 minutes.

Finally, the emulsion was cooled to room temperature, the solids contentwas corrected to 45% using demineralized water, and the pH was correctedto 7.5 using a 25 wt-% ammonia solution.

Example 18 DBI Containing s/h Sequential

To a round-bottomed flask equipped with a condenser, thermometer, and astirrer were charged 426.6 parts of demineralized water, 0.4 parts ofsodium bicarbonate, 31.3 parts of a 20 wt-% aqueous solution of aphosphate functional surfactant (Fosfodet FAZ109V, ex. KAO), and 0.4parts of a 25 wt-% ammonia solution. The reactor contents were heated to80° C., after which a solution of 0.4 parts of sodium persulphate in 7.9parts of demineralized water were added, followed by 10% of a firstmonomer feed consisting of 114.3 parts of demineralized water, 37.9parts of a 20 wt-% aqueous solution of a phosphate functional surfactant(Fosfodet FAZ109V, ex. KAO), 0.6 parts of sodium bicarbonate, 18.3 partsof acrylic acid, 420.6 parts of dibutyl itaconate, 18.3 parts of a 50wt-% solution of N-(2-methacryloyloxyethyl)ethylene urea in water (Plex6852-0 ex. Evonik), and 9.1 parts of methyl methacrylate. Due to theheat formed as a result of the polymerizing monomers, the temperaturerose to 90° C., after which adding the remainder of the first monomerfeed was started. The first monomer feed was added over a period of 45minutes. Simultaneously, 60% of an initiator feed, consisting of 36.3parts of demineralized water, 0.2 parts of sodium bicarbonate, and 2.0parts of sodium persulphate, was fed over a period of 45 minutes. At theend of the monomer feed, the feed tank was rinsed with 7.6 parts ofdemineralized water.

Next, a mixture of 0.9 parts of a 25 wt-% ammonia solution and 1.2 partsof demineralized water was fed over a period of 15 minutes. 45 minutesafter the end of the first monomer feed, a second monomer feed,consisting of 77.5 parts of demineralized water, 21.9 parts of a 20 wt-%aqueous solution of a phosphate functional surfactant (Fosfodet FAZ109V,ex. KAO), 0.4 parts of sodium bicarbonate, 7.8 parts of acrylic acid,45.0 parts of dibutyl itaconate, and 143.0 parts of methyl methacrylate,was started. This feed, and the remainder of the initiator feed that wasfed simultaneously, were added over a period of 30 minutes. Aftercompletion of the second monomer feed, the feed tank was rinsed with15.3 parts of demineralized water and the mixture was allowed to stir at90° C. for another 30 minutes.

Finally, the emulsion was cooled to room temperature, the solids contentwas corrected to 45% using demineralized water, and the pH was correctedto 7.5 using a 25 wt-% ammonia solution.

Comparative Example Comp V DBI Free s/h Sequential

To a round-bottomed flask equipped with a condenser, thermometer, and astirrer were charged 426.6 parts of demineralized water, 0.4 parts ofsodium bicarbonate, 31.3 parts of a 20 wt-% aqueous solution of aphosphate functional surfactant (Fosfodet FAZ109V, ex. KAO), and 0.4parts of a 25 wt-% ammonia solution. The reactor contents were heated to80° C., after which a solution of 0.4 parts of sodium persulphate in 7.9parts of demineralized water were added, followed by 10% of a firstmonomer feed consisting of 114.3 parts of demineralized water, 37.9parts of a 20 wt-% aqueous solution of a phosphate functional surfactant(Fosfodet FAZ109V, ex. KAO), 0.6 parts of sodium bicarbonate, 18.3 partsof acrylic acid, 420.6 parts of butyl acrylate, 18.3 parts of a 50 wt-%solution of N-(2-methacryloyloxyethyl)ethylene urea in water (Plex6852-0 ex. Evonik), and 9.1 parts of methyl methacrylate. Due to theheat formed as a result of the polymerizing monomers, the temperaturerose to 90° C., after which adding the remainder of the first monomerfeed was started. The first monomer feed was added over a period of 45minutes. Simultaneously, 60% of an initiator feed, consisting of 36.3parts of demineralized water, 0.2 parts of sodium bicarbonate, and 2.0parts of sodium persulphate, was fed over a period of 45 minutes. At theend of the monomer feed, the feed tank was rinsed with 7.6 parts ofdemineralized water. Next, a mixture of 0.9 parts of a 25 wt-% ammoniasolution and 1.2 parts of demineralized water was fed over a period of15 minutes.

45 minutes after the end of the first monomer feed, a second monomerfeed, consisting of 77.5 parts of demineralized water, 21.9 parts of a20 wt-% aqueous solution of a phosphate functional surfactant (FosfodetFAZ109V, ex. KAO), 0.4 parts of sodium bicarbonate, 7.8 parts of acrylicacid, 45.0 parts of butyl acrylate, and 143.0 parts of methylmethacrylate, was started. This feed, and the remainder of the initiatorfeed that was fed simultaneously, were added over a period of 30minutes. After completion of the second monomer feed, the feed tank wasrinsed with 15.3 parts of demineralized water and the mixture wasallowed to stir at 90° C. for another 30 minutes.

Finally, the emulsion was cooled to room temperature, the solids contentwas corrected to 45% using demineralized water, and the pH was correctedto 7.5 using a 25 wt-% ammonia solution.

To illustrate the invention, film properties were determined for aselection of the polymer emulsions described above. The polymeremulsions were formulated with 8% of butyl diglycol to make them filmforming. The films were cast, dried at ambient temperature for 4 hours,and next dried for 34 hours at 50° C. The results are shown below inTable 4.

TABLE 4 Film properties; “5” means excellent resistance properties, nodamage to the film, “1” indicated completely destroyed film Water spottest Stain resistance König 16 Blocking (16 hrs)* hardness 1 hr hrsresistance EtOH Andy Coffee (s) Ex 15 5 5 3 5 4 5 201 Comp I 5 4 1 4 2 5110 Ex 16 5 5 5 4 4 5 173 Comp II 5 3 3 3 2 4 115 Comp III Could not beprepared due to instable processing. Ex 17 5 5 5 3 4 5 70 Comp IV 5 5 33 2 4 60 Ex 18 5 5 4 3 3 5 115 Comp V 5 5 0 3 2 4 8 *Determined as spottest.

In all cases (except Comp III), the water spot was good. Blockingresistance and König hardness were in all cases better for the polymersaccording to the invention compared to their most similar comparativeexamples. While resistance to coffee and ethanol were comparable betweenpolymers according to the invention and the comparatives, the resistanceto soap (Andy) was clearly better for the polymers according to theinvention.

Example 19 MMA/DMI/AA

To a round-bottomed flask equipped with a condenser, thermometer, and astirrer are charged 394.0 parts of 2-butanone. The reactor contents areheated to 80° C. As soon as the polymerization temperature is reached,13.3 parts of azobis(2-methyl butyronitrile) are added and the monomerfeed and catalyst feed are started. The monomer feed consists of 244.4parts of methyl methacrylate, 244.4 parts of dimethyl itaconate, and244.4 parts of acrylic acid. The catalyst feed consists of 31.1 parts ofazobis(2-methyl butyronitrile) dissolved in 125.9 parts of 2-butanone.Both feeds are added over a period of 180 minutes.

At the end of the feeds 2.5 parts of azobis(2-methyl butyronitrile) areadded and the mixture is stirred at 80° C. for another 150 minutes. Themixture is cooled to room temperature.

To 615.8 parts of the polymer solution is added a mixture of 99.6 partsof a 25 wt-% of ammonia in water, and 1080.5 parts of water. Next, the2-butanone is removed at 50° C. under reduced pressure. The solidscontent is corrected to 22.5% using demineralized water and the pH iscorrected to 8.6-8.8 using a 25 wt-% solution of ammonia in water.

The final polymer solution has a solids content of 22.5% and a pH of8.7.

Example 20 S/DMI/AA

To a round-bottomed flask equipped with a condenser, thermometer, and astirrer are charged 394.0 parts of 2-butanone. The reactor contents areheated to 80° C. As soon as the polymerization temperature is reached,13.3 parts of azobis(2-methyl butyronitrile) are added and the monomerfeed and catalyst feed are started. The monomer feed consists of 244.4parts of styrene, 244.4 parts of dimethyl itaconate, and 244.4 parts ofacrylic acid. The catalyst feed consists of 31.1 parts ofazobis(2-methyl butyronitrile) dissolved in 125.9 parts of 2-butanone.Both feeds are added over a period of 180 minutes.

At the end of the feeds 2.5 parts of azobis(2-methyl butyronitrile) areadded and the mixture is stirred at 80° C. for another 150 minutes. Themixture is cooled to room temperature.

To 546.1 parts of polymer solution is added a mixture of 105.4 parts ofa 25 wt-% of ammonia in water, and 1144.1 parts of water. Next, the2-butanone is removed at 50° C. under reduced pressure. The solidscontent is corrected to 22.5% using demineralized water and the pH iscorrected to 8.6-8.8 using a 25 wt-% solution of ammonia in water.

The final polymer solution has a solids content of 22.4% and a pH of8.6.

Example 21 MMA/DMI/AA

To a high pressure reactor equipped with a thermometer, and a stirrerare charged 500.0 parts of 2-butanone. The reactor contents are heatedto 140° C. As soon as the polymerization temperature is reached, 2.9parts of di-t-butyl peroxide and 40 parts of 2-butanone are added. 5minutes later the monomer feed is started. The monomer feed consists of331.8 parts of methyl methacrylate, 331.8 parts of dimethyl itaconate,331.8 parts of acrylic acid, 5.7 parts of di-t-butyl peroxide, and 6.6parts of t-butyl perbenzoate, and is added over a period of 180 minutesat 140° C.

At the end of the feed the feed tank is rinsed with 90.9 parts of2-butanone. 45 minutes after completion of the monomer feed 2.5 parts oft-butyl perbenzoate dissolved in 40 parts of 2-butanone are added andthe mixture is stirred at 140° C. for another 45 minutes. Next, 2.5parts of t-butyl perbenzoate dissolved in 40 parts of 2-butanone areadded and the mixture is stirred for another 135 minutes at 140° C.

The mixture is cooled to room temperature.

To 619.3 parts of the polymer solution is added a mixture of 99.3 partsof a 25 wt-% of ammonia in water, and 1077.3 parts of water. Next, the2-butanone is removed at 50° C. under reduced pressure. The solidscontent is corrected to 22.5% using demineralized water and the pH iscorrected to 8.6-8.8 using a 25 wt-% solution of ammonia in water.

The final polymer solution has a solids content of 22.5% and a pH of8.6.

Example 22 S/DMI/AA

To a high pressure reactor equipped with a thermometer, and a stirrerare charged 500.0 parts of 2-butanone. The reactor contents are heatedto 140° C. As soon as the polymerization temperature is reached, 4.4parts of di-t-butyl peroxide and 40 parts of 2-butanone are added. 5minutes later the monomer feed is started. The monomer feed consists of331.8 parts of styrene, 331.8 parts of dimethyl itaconate, 331.8 partsof acrylic acid, 8.6 parts of di-t-butyl peroxide, and 10.0 parts oft-butyl perbenzoate, and is added over a period of 180 minutes at 140°C.

At the end of the feed the feed tank is rinsed with 90.9 parts of2-butanone. 45 minutes after completion of the monomer feed 2.5 parts oft-butyl perbenzoate dissolved in 40 parts of 2-butanone are added andthe mixture is stirred at 140° C. for another 45 minutes. Next, 2.5parts of t-butyl perbenzoate dissolved in 40 parts of 2-butanone areadded and the mixture is stirred for another 135 minutes at 140° C.

The mixture is cooled to room temperature.

To 617.8 parts of the polymer solution is added a mixture of 99.4 partsof a 25 wt-% of ammonia in water, and 1078.6 parts of water. Next, the2-butanone is removed at 50° C. under reduced pressure. The solidscontent is corrected to 22.5% using demineralized water and the pH iscorrected to 8.6-8.8 using a 25 wt-% solution of ammonia in water.

The final polymer solution has a solids content of 22.5% and a pH of8.7.

Example 23 Sequential Polymerization Using the Polymer from Example 44

To a round-bottomed flask equipped with a condenser, thermometer, and astirrer are charged 128.9 parts of the alkaline solution obtained fromExample 44. The mixture is heated to 80° C.±2° C.

As soon as the reaction temperature is reached, a mixture of 0.2 partsof sodium persulphate and 0.4 parts of demineralized water is added.After 5 minutes, the monomer feed, consisting of 43.8 parts of methylmethacrylate and 43.8 parts of butyl acrylate, and the initiator feed,consisting of 10.8 parts of demineralized water and 0.4 parts of sodiumpersulphate (corrected to a pH of 8 using a 25 wt-% ammonia solution)are started. Both feeds should take 120 minutes. At the end of themonomer feed, the feed tank is rinsed with 1.2 parts of water. Afterboth feeds are completed, the batch is stirred at 80° C. for another 30minutes, after which it is cooled to 50° C.

At 50° C., one third of a mixture consisting of 0.1 part of a 70 wt-%solution of t-butyl hydroperoxide is added followed by one third of asolution of 0.1 part of iso-ascorbic acid in 2.9 parts of water. 15minutes later and 30 minutes later similar portions are added and thebatch is stirred at 50° C. for another 15 minutes.

The pH is checked and, if necessary, adjusted to 8.4±0.1 using a 25 wt-%solution of ammonia in water. The batch is cooled to room temperature,after which the solids content is adjusted to 48.5%±1% usingdemineralized water.

Example 24 Sequential Polymerization Using the Polymer from Example 20

Example 24 was prepared analogously to the method described in Example23, replacing Example 19 with the alkaline solution obtained fromExample 20. The final emulsion obtained was highly viscous, requiring adilution to a solids content of 35%.

Example 25 Sequential Polymerization Using the Polymer from Example 21

Example 25 was prepared analogously to the method described in Example23, replacing Example 19 with the alkaline solution obtained fromExample 21.

Example 26 Sequential Polymerization Using the Polymer from Example 22

Example 26 was prepared analogously to the method described in Example23, replacing Example 19 with the alkaline solution obtained fromExample 22.

TABLE 5 Results SC (%) Viscosity (mPa · s) pH Example 23 47.6 208 8.4Example 24 34.8 1006 8.4 Example 25 48.1 35 8.5 Example 26 48.1 201 8.4

1. A vinyl sequential copolymer [optionally substantially free ofstyrene (<1.5 wt-% of copolymer)] the copolymer composition comprising:(a) at least 23% by weight of at least one monomer represented byFormula 1

where both R₁ and R₂ independently represent an optionally substitutedhydrocarbo moiety having from 4 to 10 carbon atoms. (b) optionally atleast one hydrophilic monomer also in an amount sufficient that theresultant polymer has an acid value less than 150 mg KOH per g ofpolymer, (c) optionally of one or more monomers represented by Formula 2

where R₃ and R₄ independently represent H or an optionally substitutedhydrocarbo moiety having from 1 to 20 carbon atoms X₁ and X₂independently represents O or NR₅ where R₅ denotes H or an optionallysubstituted hydrocarbo moiety having from 1 to 20 carbon atoms with theproviso that when X₁ and/or X₂ are 0 then the respective R₃ and/or R₄attached to the oxy group independently represent an optionallysubstituted hydrocarbo having from 1 to 3 carbon atoms (d) optionallyless than 77% by weight of monomers other than components (a), (b) or(c). where the percentages or amounts of (a), (b) (c) (d) are by weightcalculated as a proportion of the total weight of (a)+(b)+(c)+(d) andthus total 100%; where independently at least one of the components(a),(b) (c) and/or (d) and/or the copolymer obtained from them arebiorenewable defined as comprising an amount of carbon-14 sufficient toproduce a decay of at least about 1.5 dpm/gC (disintegrations per minuteper gram carbon).
 2. A copolymer as claimed in claim 1, in which (a)component (a) is from 24% to 70% by weight of one or more monomersrepresented by Formula 1 (b) component (b) is one or more acidfunctional monomer(s) in an amount from 0.5% to 15% by weight, in anamount also sufficient that the resultant polymer has an acid value offrom 3 to 100 mg KOH per g of polymer, (c) component (c) is from 0.01%to 10% by weight of one or more monomers represented by Formula 2 inwhich X₁ and X₂ are both O and R₃ and/or R₄ independently represent anoptionally substituted hydrocarbo having from 1 to 3 carbon atoms. (d)component (d) if present is less than 75% wt-% by weight of monomer(s)other than components (a), (b) or (c) and does not contain stryene.butyl acrylate, 2-ethyl hexyl acrylate and/or mixtures thereof; wherethe weight percentages or amounts of (a), (b) (c) (d) are calculated asa proportion of the total amount of (a)+(b)+(c)+(d) which thus totals100%; with the provisos that where the copolymer is prepared by anemulsion polymerisation a chaser monomer is not used; the copolymer isnot prepared in the presence of a seed polymer comprising apoly(itaconate ester); the copolymer is not prepared in the presence ofan initiator system comprising an organoborane amine complex.
 3. Acopolymer as claimed in claim 1, in which component (a) comprisesdibutyl itaconate;
 4. A copolymer as claimed in claim 1, in which: (a)component (a) is present in an amount of from 30 to 65 wt-% and isdibutyl itaconate; (b) optional component (b) if present is present inan amount of up to 10 wt-% and comprises an acid functionalethylenically unsaturated monomer and/or anhydride thereof; (c) optionalcomponent (c) if present is present in an amount of from 1 to 25 wt-%and is dimethyl itaconate and/or diethyl itaconate; (d) optionalcomponent (d) if present is present in an amount such that (a) and (d)[and (b) and (c) where present] total 100% by weight.
 5. A copolymer asclaimed in claim 1 in which: component (d) comprises at least onepolymer precursor(s) of Formula 3

where Y denotes an electronegative group, R₆ is H, OH or an optionallyhydroxy substituted C₁₋₁₀hydrcarbo R₇ is H or a C₁₋₁₀hydrocarbo; R₈ is aC₁₋₁₀hydrocarbo group substituted by at least one activated unsaturatedmoiety; and; either: A represents a divalent organo moiety attached toboth the —HN— and —Y— moieties so the —A—, —NH—, —C(═O)— and —Y—moieties together represent a ring of 4 to 8 ring atoms, and R₇ and R₈are attached to any suitable point on the ring; or A is not present (andFormula 3 represents a linear and/or branched moiety that does notcomprise a heterocyclic ring) in which case R₇ and R₈ are attached toR₆; and m is an integer from 1 to
 4. 6. A process for preparing acopolymer as claimed in claim 1 and/or the process comprising the stepof polymerising polymer precursors in a sequential polymerisation methodthe polymer precursors comprising component (a), component (b) andoptionally components (c) and/or component (d) to obtain a sequentialcopolymer, where optionally the polymerisation method is selected fromaqueous emulsion polymerisation and suspension polymerisation and wherethe method does not comprise a chaser monomer step.
 7. A copolymerobtained and/or obtainable by a process according to claim
 6. 8. Acoating composition comprising a copolymer as claimed in claim
 1. 9. Asubstrate and/or article having coated thereon an (optionally cured)coating composition of claim
 8. 10. A method of using a copolymer asclaimed in claim 1 to prepare a coating composition.
 11. A method forpreparing a coated substrate and/or article comprising the steps ofapplying a coating composition of claim 8 to the substrate and/orarticle and optionally curing said composition in situ to form a curedcoating thereon.